Resistance change memory and manufacturing method thereof

ABSTRACT

According to one embodiment, a resistance-change memory of embodiment includes a first interconnect line extending in a first direction, a second interconnect line extending in a second direction intersecting with the first direction, and a cell unit. The cell unit is provided at an intersection of the first interconnect line and the second interconnect line. The cell unit includes a non-ohmic element having a silicide layer on at least one of first and second ends thereof, and a memory element to store data in accordance with a reversible change in a resistance state. The silicide layer includes a 3d transition metal element which combines with an Si element to form silicide and which has a first atomic radius, and at least one kind of an additional element having a second atomic radius greater than the first atomic radius.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is based upon and claims the benefit of priority fromJapanese Patent Application No. 2009-272628, filed Nov. 30, 2009; theentire contents of which are incorporated herein by reference.

FIELD

Embodiments described herein relate generally to a resistance changememory and a manufacturing method thereof.

BACKGROUND

Recently, as next-generation nonvolatile semiconductor memories,resistance change memories have been attracting attention, such as aresistive RAM (ReRAM) in which a variable resistive element serves as amemory element, and a phase change RAM (PCRAM) in which a phase changeelement serves as a memory element.

These resistance change memories are characterized in that a memory cellarray is a cross-point type and a higher memory capacity is enabled bythree-dimensional integration, and also characterized by being capableof the same high-speed operation as that of a DRAM.

If such a resistance change memory is put to practice use, a NAND flashmemory serving as a file memory and a DRAM serving as a work memory, forexample, can be replaced with the resistance change memories.

There are, however, challenges to solve in putting the resistance changememory to practice use. One of these challenges concerns the material(e.g., silicide) used for the resistance change memory.

Jpn. Pat. Appln. KOKAI Publication No. 2005-019943 discloses a techniqueassociated with nickel silicide to which other elements are added.

However, the use of silicide that takes the structure and manufacturingprocess of the resistance change memory is desired.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram showing a resistance change memory;

FIG. 2 is a diagram showing an example of the configuration of a memorycell array in the resistance change memory;

FIG. 3 is a diagram showing a cell unit of the resistance change memoryaccording to an embodiment;

FIG. 4 is a graph for illustrating the characteristics of silicideincluded in the cell unit according to the present embodiment;

FIG. 5A is a graph for illustrating the characteristics of silicideincluded in the cell unit according to the present embodiment;

FIG. 5B is a graph for illustrating the characteristics of silicideincluded in the cell unit according to the present embodiment;

FIG. 6A is a graph for illustrating the characteristics of silicideincluded in the cell unit according to the present embodiment;

FIG. 6B is a view for illustrating the characteristics of silicideincluded in the cell unit according to the present embodiment;

FIG. 7A is a graph for illustrating the characteristics of silicideincluded in the cell unit according to the present embodiment;

FIG. 7B is a graph for illustrating the characteristics of silicideincluded in the cell unit according to the present embodiment;

FIG. 8A is a diagram for illustrating the characteristics of silicideincluded in the cell unit according to the present embodiment;

FIG. 8B is a graph for illustrating the characteristics of silicideincluded in the cell unit according to the present embodiment;

FIG. 9 is a diagram showing an example of the configuration of the cellunit;

FIG. 10 is a diagram showing the connection between a memory element anda rectification element;

FIG. 11A is a diagram showing the layout of first and second controlcircuits;

FIG. 11B is a diagram showing the layout of the first and second controlcircuits;

FIG. 11C is a diagram showing the layout of the first and second controlcircuits;

FIG. 12A is a diagram showing an example of the configuration of thecell unit;

FIG. 12B is a diagram showing an example of the configuration of thecell unit;

FIG. 12C is a diagram showing an example of the configuration of thecell unit;

FIG. 12D is a diagram showing an example of the configuration of thecell unit;

FIG. 12E is a diagram showing an example of the configuration of thecell unit;

FIG. 12F is a diagram showing an example of the configuration of thecell unit;

FIG. 13A is a diagram showing an example of the configuration of anon-ohmic element;

FIG. 13B is a diagram showing an example of the configuration of thenon-ohmic element;

FIG. 13C is a graph for illustrating the work function of silicide;

FIG. 14A is a diagram showing one step of a first method ofmanufacturing the resistance change memory according to the embodiment;

FIG. 14B is a diagram showing one step of the first method ofmanufacturing the resistance change memory according to the embodiment;

FIG. 14C is a diagram showing one step of the first method ofmanufacturing the resistance change memory according to the embodiment;

FIG. 14D is a diagram showing one step of the first method ofmanufacturing the resistance change memory according to the embodiment;

FIG. 14E is a diagram showing one step of the first method ofmanufacturing the resistance change memory according to the embodiment;

FIG. 14F is a diagram showing one step of the first method ofmanufacturing the resistance change memory according to the embodiment;

FIG. 14G is a diagram showing one step of the first method ofmanufacturing the resistance change memory according to the embodiment;

FIG. 14H is a diagram showing one step of the first method ofmanufacturing the resistance change memory according to the embodiment;

FIG. 15A is a diagram showing one step of a second method ofmanufacturing the resistance change memory according to the embodiment;

FIG. 15B is a diagram showing one step of the second method ofmanufacturing the resistance change memory according to the embodiment;

FIG. 15C is a diagram showing one step of the second method ofmanufacturing the resistance change memory according to the embodiment;

FIG. 15D is a diagram showing one step of the second method ofmanufacturing the resistance change memory according to the embodiment;

FIG. 16A is a diagram showing one step of a third method ofmanufacturing the resistance change memory according to the embodiment;

FIG. 16B is a diagram showing one step of the third method ofmanufacturing the resistance change memory according to the embodiment;

FIG. 16C is a diagram showing one step of the third method ofmanufacturing the resistance change memory according to the embodiment;

FIG. 16D is a diagram showing one step of the third method ofmanufacturing the resistance change memory according to the embodiment;

FIG. 17A is a diagram showing one step of a fourth method ofmanufacturing the resistance change memory according to the embodiment;

FIG. 17B is a diagram showing one step of the fourth method ofmanufacturing the resistance change memory according to the embodiment;

FIG. 18A is a diagram showing one step of a fifth method ofmanufacturing the resistance change memory according to the embodiment;

FIG. 18B is a diagram showing one step of the fifth method ofmanufacturing the resistance change memory according to the embodiment;

FIG. 19 is a diagram for illustrating the operation of the resistancechange memory;

FIG. 20A is a diagram showing a modification of the resistance changememory according to the embodiment;

FIG. 20B is a diagram showing the modification of the resistance changememory according to the embodiment;

FIG. 21A is a diagram showing a modification of the resistance changememory according to the embodiment;

FIG. 21B is a diagram showing the modification of the resistance changememory according to the embodiment;

FIG. 21C is a diagram showing the modification of the resistance changememory according to the embodiment;

FIG. 22 is a diagram for illustrating a structure according to theapplication;

FIG. 23 is a diagram for illustrating a manufacturing method accordingto the application;

FIG. 24 is a diagram for illustrating a structure according to theapplication;

FIG. 25A is a diagram for illustrating a structure according to theapplication;

FIG. 25B is a diagram for illustrating a structure according to theapplication; and

FIG. 26 is a diagram for illustrating a manufacturing method accordingto the application.

DETAILED DESCRIPTION

Hereinafter, an embodiment of embodiments will be described in detailwith reference to the drawings. In the following explanation, elementshaving the same function and configuration are provided with the samesigns and are repeatedly described when necessary.

In general, according to one embodiment, a resistance change memoryincludes a first interconnect line extending in a first direction, asecond interconnect line extending in a second direction intersectingwith the first direction; and a cell unit. The cell unit is provided atan intersection of the first interconnect line and the secondinterconnect line. The cell unit includes a non-ohmic element having asilicide layer on at least one of first and second ends thereof, and amemory element to store data in accordance with a reversible change in aresistance state. The silicide layer includes a 3d transition metalelement which combines with an Si element to form silicide and which hasa first atomic radius, and at least one kind of an additional elementhaving a second atomic radius greater than the first atomic radius.

The embodiment is directed to a resistance change memory in which avariable resistive element or a phase change element serves as a memoryelement.

Embodiment Basic Example

(1) Configuration

A resistance change memory according to an embodiment of the embodimentis described with FIG. 1 to FIG. 3.

FIG. 1 shows essential parts of the resistance change memory.

A resistance change memory (e.g., chip) 1 has a memory cell array 2.

A first control circuit 3 is disposed at one end of the first directionof memory cell array 2, and a second control circuit 4 is disposed atthe other end of the second direction that intersects with the firstdirection.

The first control circuit 3 selects a row of the memory cell array 2 onthe basis of, for example, a row address signal. Moreover, the secondcontrol circuit 4 selects a column of the memory cell array 2 on thebasis of, for example, a column address signal.

The first and second control circuit 3, 4 control writing, erasing andreading of data in a memory element within memory cell array 2.

Here, in the resistance change memory 1, for example, a write isreferred to as a set, and an erasure is referred to as a reset. Aresistance value in a set state has only to be different from aresistance value in a reset state, and whether the resistance value inthe set state is higher or lower makes no difference.

Moreover, if one of a plurality of levels of resistance values that canbe marked by the memory element can be selectively written in a setoperation, a multilevel resistance change memory in which one memoryelement stores multilevel data can be obtained.

A controller 5 supplies a control signal and data to the resistancechange memory 1. The control signal is input to a command/interfacecircuit 6, and data is input to a data input/output buffer 7. Thecontroller 5 may be disposed in the chip 1 or may be disposed in a chip(host device) different from the chip 1.

The command/interface circuit 6 judges in accordance with the controlsignal whether data from the controller 5 is command data. When the datais command data, the data is transferred from the data input/outputbuffer 7 to a state machine 8.

The state machine 8 manages the operation of the resistance changememory 1 on the basis of the command data. For example, the statemachine 8 manages the set/reset operations and read operation on thebasis of command data from the controller 5. The controller 5 canreceive status information managed by the state machine 8, and judge theresult of the operation in the resistance change memory 1.

In the set/reset operations and read operation, the controller 5supplies an address signal to the resistance change memory 1. Theaddress signal is input to the first and second control circuits 3, 4via the address buffer 9.

A potential supplying circuit 10 outputs, at a predetermined timing, avoltage pulse or current pulse necessary for, for example, the set/resetoperations and read operation in accordance with an instruction from thestate machine 8. The potential supplying circuit 10 includes a pulsegenerator 10A.

FIG. 2 is a bird's-eye view showing the structure of the memory cellarray. The memory cell array shown in FIG. 2 has a cross-point typestructure.

The cross-point type memory cell array 2 is disposed on a substrate 11.The substrate 11 is a semiconductor substrate (e.g., a siliconsubstrate), or an interlayer insulating film on a semiconductorsubstrate. In addition, when the substrate 11 is an interlayerinsulating film, a circuit that uses, for example, a field effecttransistor may be formed on the surface of a semiconductor substrateunder the cross-point type memory cell array 2.

The cross-point type memory cell array 2 is configured by, for example,a stack structure of a plurality of memory cell arrays (also referred toas memory cell layers).

FIG. 2 shows, by way of example, the case where the cross-point typememory cell array 2 is composed of four memory cell arrays M1, M2, M3,M4 that are stacked in the third direction (a direction perpendicular tothe main plane of substrate 11). The number of memory cell arraysstacked has only to be two or more. In addition, the cross-point typememory cell array 2 may be configured by one memory cell array.Alternatively, an insulating film may be provided between two memorycell arrays stacked, and the two memory cell arrays may be electricallyseparated by the insulating film.

Thus, when the plurality of memory cell arrays M1, M2, M3, M4 arestacked, the address signal includes, for example, a memory cell arrayselection signal, a row address signal and a column address signal. Thefirst and second control circuit 3, 4 select one of the stacked memorycell arrays in accordance with, for example, the memory cell arrayselection signal. The first and second control circuit 3, 4 canwrite/erase/read data in one of the stacked memory cell arrays, or cansimultaneously write/erase/read data in two or more or all of thestacked memory cell arrays.

Memory cell array M1 is composed of a plurality of cell units CU1arrayed in the first and second directions. Similarly, the memory cellarray M2 is composed of a plurality of arrayed cell units CU2, memorycell array M3 is composed of a plurality of arrayed cell units CU3, andmemory cell array M4 is composed of a plurality of arrayed cell unitsCU4.

Each of cell units CU1, CU2, CU3, CU4 is composed of a memory elementand a non-ohmic element that are connected in series.

Furthermore, on the substrate 11, there are arranged, from the side ofthe substrate 11, interconnect lines L1 (j−1), L1 (j), L1 (j+1),interconnect lines L2 (i−1), L2 (i), L2 (i+1), interconnect lines L3(j−1), L3 (j), L3 (j+1), interconnect lines L4 (i−1), L4 (i), L4 (i+1),and interconnect lines L5 (j−1), L5 (j), L5 (j+1).

The odd interconnect lines from the side of substrate 11, that is,interconnect lines L1 (j−1), L1 (j), L1 (j+1), interconnect lines L3(j−1), L3 (j), L3 (j+1) and interconnect lines L5 (j−1), L5 (j), L5(j+1) extend in the second direction.

The even interconnect lines from the side of substrate 11, that is,interconnect lines L2 (i−1), L2 (i), L2 (i+1) and interconnect lines L4(i−1), L4 (i), L4 (i+1) extend in the first direction.

These interconnect lines are used as word lines or bit lines. Here,interconnect lines L1 (j−1), L1 (j), L1 (j+1), L3 (j−1), L3 (j), L3(j+1), L5 (j−1), L5 (j), L5 (j+1) that extend in the second directionintersect with interconnect lines L2 (i−1), L2 (i), L2 (i+1), L4 (i−1),L4 (i), L4 (i+1) that extend in the first direction.

Lowermost first memory cell array M1 is disposed between firstinterconnect lines L1 (j−1), L1 (j), L1 (j+1) and second interconnectlines L2 (i−1), L2 (i), L2 (i+1). In the set/reset operations and readoperation for the memory cell array M1, either interconnect lines L1(j−1), L1 (j), L1 (j+1) or interconnect lines L2 (i−1), L2 (i), L2 (i+1)are used as word lines, and the other interconnect lines are used as bitlines.

The memory cell array M2 is disposed between second interconnect linesL2 (i−1), L2 (i), L2 (i+1) and third interconnect lines L3 (j−1), L3(j), L3 (j+1). In the set/reset operations and read operation for thememory cell array M2, either interconnect lines L2 (i−1), L2 (i), L2(i+1) or interconnect lines L3 (j−1), L3 (j), L3 (j+1) are used as wordlines, and the other interconnect lines are used as bit lines.

The memory cell array M3 is disposed between third interconnect lines L3(j−1), L3 (j), L3 (j+1) and fourth interconnect lines L4 (i−1), L4 (i),L4 (i+1). In the set/reset operations and read operation for the memorycell array M3, either interconnect lines L3 (j−1), L3 (j), L3 (j+1) orinterconnect lines L4 (i−1), L4 (i), L4 (i+1) are used as word lines,and the other interconnect lines are used as bit lines.

The memory cell array M4 is disposed between fourth interconnect linesL4 (i−1), L4 (i), L4 (i+1) and fifth interconnect lines L5 (j−1), L5(j), L5 (j+1). In the set/reset operations and read operation for thememory cell array M4, either interconnect lines L4 (i−1), L4 (i), L4(i+1) or interconnect lines L5 (j−1), L5 (j), L5 (j+1) are used as wordlines, and the other interconnect lines are used as bit lines.

FIG. 3 is a bird's-eye view schematically showing the structure of onecell unit.

In the cross-point type memory cell array 2, a current is only passedthrough a selected memory element, a memory element 20 and a non-ohmicelement 30 are connected in series between two interconnect lines (theword line and the bit line).

In the cell unit CU in FIG. 3, the memory element 20 is stacked on thenon-ohmic element 30. However, the structure of the cell unit CU shownin FIG. 3 is only one example, and the non-ohmic element 30 may bestacked on the memory element 20.

In the cross-point type memory cell array, a stack composed of thememory element 20 and the non-ohmic element 30 is disposed as one cellunit CU in a part where two interconnect lines 60, 65 intersect witheach other. In the stacking direction (third direction), the cell unitCU is interposed between two interconnect lines 60, 65. Here,interconnect lines 60, 65 correspond to two successively stackedinterconnect lines in FIG. 2, such as interconnect line L1 (j) andinterconnect line L2 (i), or interconnect line L2 (i) and interconnectline L3 (j) or interconnect line L3 (j) and interconnect line L4 (i).

The memory element 20 is a variable resistive element or a phase changeelement. Here, the term variable resistive element means an element madeof a material with a resistance value that changes upon application of,for example, a voltage, a current or heat. The term phase change elementmeans an element made of a material having a physicality (impedance)such as a resistance value or capacitance that changes due to a phasechange by an application of a voltage, a current or heat.

The term phase change (phase transition) includes the following:

-   -   Metal-semiconductor transition, metal-insulator transition,        metal-metal transition, insulator-insulator transition,        insulator-semiconductor transition, insulator-metal transition,        semiconductor-semiconductor transition, semiconductor-metal        transition, semiconductor-insulator transition    -   Phase change of quantum state (e.g., metal-superconductor        transition)    -   Paramagnet-ferromagnet transition, antiferromagnet-ferromagnet        transition, ferromagnet-ferromagnet transition,        ferrimagnet-ferromagnet transition, or combination of the above        transitions    -   Paraelectric-ferromagnet transition, paraelectric-pyroelectric        transition, paraelectric-piezoelectric transition,        ferroelectric-ferroelectric transition,        antiferroelectric-ferroelectric transition, or combination of        the above transitions    -   Combination of the above transitions

For example, transition to ferroelectric-ferromagnet from a metal,insulator, semiconductor, ferroelectric, paraelectric, pyroelectric,piezoelectric, ferromagnet, ferrimagnet, helimagnet, paramagnet orantiferromagnet, and reverse transition

In accordance with the above definition, the variable resistive elementincludes the phase change element.

In the embodiment of the present invention, the variable resistiveelement is mainly made of, for example, a metal oxide (e.g., a binary orternary metal oxide), a metal compound, a chalcogenide material (e.g.,Ge—Sb—Te, In—Sb—Te), organic matter, carbon, or carbon nanotube.

In addition, the resistance value of a magnetoresistive effect elementused for a magnetoresistive RAM (MRAM) changes when the relativedirections of the magnetizations of two magnetic layers constitutingthis element change. In the present embodiment, a magnetoresistiveeffect element such as a magnetic tunnel junction (MTJ) element is alsoincluded in the variable resistive element.

As a means of changing the resistance value of the memory element 20,there are an operation called a bipolar operation and an operationcalled a unipolar operation. In the bipolar operation, the polarity of avoltage applied to the memory element 20 is changed to cause areversible change in the resistance value of the memory element 20between at least a first value (first level) and a second value (secondlevel). In the unipolar operation, one or both of the intensity andapplication time (pulse width) of a voltage is controlled withoutchanging the polarity of the voltage applied to the memory element tocause a reversible change in the resistance value of the memory elementbetween at least the first value and the second value.

The bipolar operation is used for a memory such as a spin injection typeMRAM which requires bi-directional passage of a current through thememory element during writing.

The non-ohmic element 30 is an element which does not have linearity inits input/output characteristics, that is, an element which hasnon-ohmic characteristics.

A rectification element such as a PN junction diode, a PIN junctiondiode, a Schottky diode or a metal-insulator-semiconductor (MIS) diodeis used for the non-ohmic element 30. The term PN junction diode means adiode in which a P-type semiconductor layer (anode layer) and an N-typesemiconductor layer (cathode layer) form a PN junction. The term PINdiode means a diode which has an intrinsic semiconductor layer between aP-type semiconductor layer (anode layer) and an N-type semiconductorlayer (cathode layer). The term Schottky diode means a diode in which asemiconductor layer and a metal layer form a Schottky junction. The termMIS diode means a diode which has an insulating layer between a metallayer and a semiconductor layer.

In addition to the rectification element, a stack structure such as asemiconductor-insulator-semiconductor (SIS) structure or ametal-insulator-metal (MIM) structure is used for non-ohmic element 30.

In the resistance change memory driven by the unipolar operation, arectification element such as a diode is mainly used as the non-ohmicelement 30. In the resistance change memory driven by the bipolaroperation, the MIM structure or SIS structure is mainly used as thenon-ohmic element 30.

In the present embodiment, a resistance change memory that utilizes theunipolar operation is mainly described. However, it goes without sayingthat the resistance change memory in the embodiment of the presentinvention may be a memory that utilizes the bipolar operation.

When a resistance change memory having a cross-point type memory cellarray (hereinafter referred to as a cross-point type resistance changememory) is driven via unipolar operation, the following characteristicsare required for rectification element 30 as a non-ohmic element inorder to accurately perform the set/reset operations and read operation:a current (forward current) is high when a forward bias is applied, anda current (reverse current) is low and a breakdown voltage is high whena reverse bias is applied.

As shown in FIG. 3, in the resistance change memory according to thepresent embodiment, the non-ohmic element 30 that forms the cell unit CUhas a silicide layer 39 on at least one of its ends (upper end and lowerend) in its as-stacked direction.

The silicide layer (also simply referred to as silicide) 39 includes asilicon element 50, a 3d transition metal element 51 having first atomicradius r1, and an element 52 having second atomic radius r2. Althoughthree kinds of elements 50, 51, 52 are randomly arranged in the silicidelayer 39 in FIG. 3 for the sake of simplicity in illustration, it goeswithout saying that the three kinds of elements 50, 51, 52 arechemically bonded together on the basis of a stoichiometric compositionratio to form one crystal grain or one layer.

The 3d transition metal element 51 is chemically bonded the Si element50, and thereby the silicide layer is formed.

In the present embodiment, the 3d transition metal element 51 means ametal element capable of having stable unpaired electrons on the 3dorbit of an atom. 3d transition metal element includes, for example,scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese(Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) and zinc (Zn). Inthe present embodiment, the group of elements listed here as 3d thetransition metal elements are referred to as a 3d transition metalelement group (first element group).

The element 51 included in the silicide layer 39 is at least one kind ofelement selected from the 3d transition metal element group.

The element 52 has atomic radius r2 greater than atomic radius r1 of aselected 3d transition metal element. The element 52 having atomicradius r2 is an element added to silicide formed of the Si element andthe 3d transition metal element, and is an element foreign to silicide.In the present embodiment, the element 52 is also referred to as anadditional element or foreign element.

The element 52 includes a 4d transition metal element, a 4f transitionmetal element, a group 13 element and a group 14 element.

In the present embodiment, the 4d transition metal element means a metalelement capable of having stable unpaired electrons on the 4d orbit ofan atom. A 4d transition metal element includes, for example, yttrium(Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc),ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag) and cadmium(Cd).

In the present embodiment, the 4f transition metal element means a metalelement capable of having a stable unpaired electron on the 4f orbit ofan atom.

4f transition metal element includes, for example, lanthanum (La),cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm),samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium(Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium(Lu), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium(Os), iridium (Ir), platinum (Pt) and gold (Au).

The group 13 element includes, for example, indium (In) and thallium(T1). The group 14 element includes, for example, germanium (Ge), tin(Sn) and lead (Pb).

A group of elements 52 having an atomic radius greater than the atomicradius of an element selected as the 3d transition metal element 51 isreferred to as an additional element group (second element group). Atleast one kind is selected from the second element group for the element52 included in silicide layer 39.

The element 52 is not limited to the elements belonging to theadditional element group shown here by way of example. The element 52may be any element as long as atomic radius r2 of the element 52 isgreater than atomic radius r1 of one kind of the 3d transition metalelement 51 selected from the 3d transition metal element group.Moreover, an element belonging to the 3d transition metal element groupmay be used for the additional element 52 as long as it has as atomicradius greater than atomic radius r1 of the element 51 selected as the3d transition metal element to form silicide.

It is to be noted that, in the present embodiment, the atomic radius ofan element is regulated by one of a metallic bond radius, an ionicradius and a covalent bond radius in accordance with the selectedelement 52 and a combination state of elements. Here, the atomic radiusof each element is not described in detail. In general, the radius of anelement (atom) having a greater atomic number in the periodic table ofelements among elements of the same group tends to be greater, and theradius of an element having a smaller atomic number among elements ofthe same period tends to be greater.

The element 52 is mainly lattice-substituted for the 3d transition metalelement 51 in the crystal structure of silicide formed of the Si element50 and the 3d transition metal element 51 and present in the silicidelayer 39. That is, the silicide layer 39 including the additionalelement 52 is rendered a mixed crystal by the addition of the additionalelement 52.

However, the additional element 52 may be present in the silicide layer39 as a crystal grain of a compound of this element 52 and the Sielement 50, as a crystal grain of a compound of this element 52 and the3d transition metal element 51, as a compound of this element and twoelements 50, 51, or as a crystal grain of single additional element 52.

The silicide 39 included in the resistance change memory according tothe present embodiment is represented by a chemical formula (compositionformula) “M_(1-x)D_(x)Si_(y)”, wherein “M” indicates the 3d transitionmetal element, “D” indicates an element having a greater atomic radiusthan that of the 3d transition metal element, and “Si” indicatessilicon. Here, “x” is 0.01 or more and 0.99 or less, and “y” is 1 ormore and 2 or less.

However, silicide made of the 3d transition metal element 51 and the Sielement 52 is preferably the main component (base material) of thesilicide layer 39, and preferably has a relation x1>x2 when indicated by“x=x2”, “x1=1−x=1−x2”, that is, when indicated by M_(x1)D_(x2)Si_(y).

More specifically, the amount of addition of additional element D tosilicide composed of the Si element and 3d transition metal element (M)(the ratio of element D to element M) is preferably 30 atomic % or less.That is, the value of “x” in the composition formula of silicide in thepresent embodiment is preferably 0.3 or less.

This is based on the following theory: If element “D(52)” is excessivelyadded, a compound containing the additional element may also beexcessively generated in the silicide layer 39. Due to the excessivelyformed compound, the crystal phase of the silicide layer 39 may berough, or phase separation may be caused. Therefore, the resultingformation of no silicide layer having predetermined characteristics andconsiderable deterioration of the quality of the silicide layer 39should be prevented.

Furthermore, the additional element 52 is preferably an element which isone or more periods away from the selected 3d transition metal element51. For example, when Ti or Ni is selected as the 3d transition metalelement 51, Pd or Pt is preferably used as the additional element 52.

The reason for this is that, as described above or as represented by thecomposition formula, the added element “D(52)” is lattice-substitutedfor the 3d transition metal element in the crystal structure of silicideand the silicide layer 39 is rendered a mixed crystal. Therefore, thecrystal structure of a compound (e.g., silicide) formed of the addedelement 52 and the Si element 50 and the crystal structure of a compoundcontaining the additional element 52 are preferably approximate to thecrystal structure of silicide formed of the Si element 50 and the 3dtransition metal element 51.

For example, in the case of an MnP crystal structure as in NiSi, anelement (e.g., Pt or Pd) in which silicide formed of Si and anadditional element can have a crystal structure approximate to the MnPstructure is preferably selected as the element 52 to be added tosilicide serving as the base material.

The change in the composition and crystal structure of the silicidelayer caused by the addition of the foreign element 52 is thus takeninto consideration to prevent the adverse effect of the addition of theforeign element 52.

As shown in FIG. 3, in the resistance change memory according to theembodiment of the present invention, the silicide layer 39 whichincludes the Si element 50, the 3d transition metal element 51 formingsilicide, and the element 52 having the atomic radius r2 greater thanthe atomic radius r1 of the element 51 is provided on at least one endof the non-ohmic element (e.g., a rectification element) forming theresistance change memory.

When the foreign element 52 is added to a certain silicide, the silicidelayer 39 has high heat resistance, and characteristic deterioration ofthe junction of the silicide layer 39 and some other parts is reduced.

Thus, according to the resistance change memory in the embodiment of thepresent invention, the characteristics of elements constituting theresistance change memory, for example, the forward bias/reverse bias ofa diode can be improved.

(2) Characteristics of Silicide

The characteristics of silicide included in the resistance change memoryaccording to the embodiment of the present invention are next describedwith FIG. 4 to FIG. 8B.

FIG. 4 is a graph showing the relation between the temperature of athermal treatment for silicide and the electric resistance of silicide,in silicide included in the resistance change memory according to thepresent embodiment. In FIG. 4, the horizontal axis indicates heatingtemperature (denoted by “A” in FIG. 4, unit: ° C.), and the verticalaxis indicates electric resistance (denoted by “B” in FIG. 4). In FIG.4, the electric resistance is indicated by sheet resistance (unit: Ω/□).

In FIG. 4, the characteristics of silicide to which palladium (Pd) isadded and the characteristics of silicide to which platinum (Pt) isadded are shown. Silicide serving as the base material is nickelsilicide (NiSi_(y) (0<y≦2)). In this case, in FIG. 3, Ni corresponds tothe 3d transition metal element 51, and Pd or Pt corresponds to theadditional element 52. NiSi_(y) including Pd or Pt is formed on B-dopedSiGe. Here, silicide is thermally treated by a rapid thermal annealing(RTA) method.

In FIG. 4, the concentrations of Pd are 8 atomic %, 15 atomic % and 30atomic %, and the concentrations of Pt are 8 atomic % and 15 atomic %.

In the present embodiment, the concentrations (atomic percentages) of Pdand Pt are regulated by the ratio of Pd (or Pt) to Ni. In the presentembodiment, this ratio is indicated by atomic percent, and written asatomic % or at. %. For example, when the concentration of Pd is 8 atomic%, NiSi_(y) including Pd is indicated by Ni_(0.92)Pd_(0.08)Si_(y)(0<y≦2).

As shown in FIG. 4, at a thermal treatment temperature ranging from 500°C. to 700° C., the sheet resistance of NiSi_(y) to which Pd is added andthe sheet resistance of NiSi_(y) to which Pt is added respectively showvalues ranging from 10Ω/□ to 30Ω/□ without any significant change in theresistance value.

If agglomeration of a metal in the silicide layer or phase separation ofthe silicide layer is caused, the electric resistance (sheet resistance)of the silicide layer is increased.

Therefore, the experimental result in FIG. 4 shows that even if NiSi_(y)to which Pd or Pt is added is thermally treated at 500° C. to 700° C.,there is no agglomeration of metal elements (Ni, Pd and Pt) in thesilicide layer, no phase separation of silicide and no deterioration ofthe crystallinity of the silicide layer.

In particular, the electric resistance of NiSi_(y) to which 8 atomic %of Pd and 15 atomic % of Pd is added maintains the same level as theresistance value at a heating temperature of 500° C. to 700° C. even ifsuch NiSi_(y) is thermally treated at 750° C.

In addition, the sheet resistance of Pd-added NiSi_(y) thermally treatedat 500° C. to 700° C. is lower than the sheet resistance of Pd-addedNiSi_(y) thermally treated at 350° C. This is attributed to the factthat the crystallinity of silicide has improved owing to the thermaltreatment or a chemical reaction between the metal (Ni, Pd) elements andthe Si element is optimized within a temperature range of 500° C. to700° C. such that the composition ratio of silicide made of Ni, Pd andSi is closer to an ideal stoichiometric composition ratio.

On the other hand, the resistance value of NiSi_(y) to which Pt is addedis within a range of 350° C. to 700° C., and shows no great change. Itis considered from this fact that the reaction temperature forsilicidation of NiSi_(Y) containing Pt (hereinafter also referred to asa silicide reaction temperature) is lower than the silicide reactiontemperature of NiSi_(x) containing Pd.

FIG. 5A and FIG. 5B show changes in the electric resistance of silicideincluded in the resistance change memory according to the presentembodiment versus the concentration of the element (foreign element)added to silicide. In FIG. 5A and FIG. 5B, the horizontal axis indicatesthe concentration (denoted by “A” in FIG. 5A and FIG. 5B) of the addedelement, and the vertical axis indicates electric resistance (here,sheet resistance) (denoted by “B” in FIG. 5A and FIG. 5B). The unit ofthe concentration of the added element is at. % (atomic %).

FIG. 5A and FIG. 5B show the cases where Pd or Pt is added to NiSi_(y)as in the example shown in FIG. 4. In addition, each silicide layer isformed on B-doped SiGe as in FIG. 4.

FIG. 5A shows the case where NiSi_(Y) to which Pd or Pt is added isthermally treated at 700° C. FIG. 5B shows the case where NiSi_(y) towhich Pd or Pt is added is thermally treated at 750° C.

As shown in FIG. 5A and FIG. 5B, the sheet resistance of Pd-addedNiSi_(y) is lower than the sheet resistance of Pt-added NiSi_(y).

Moreover, as in FIG. 4, the sheet resistance of Pt-added NiSi_(y) at aheating temperature of 750° C. is higher than the sheet resistance at aheating temperature of 700° C. On the other hand, the sheet resistanceof Pd-added NiSi_(Y) even at a heating temperature reaching 750° C. isat about the same level as the sheet resistance at a heating temperatureof 700° C.

Further, in Pd-added NiSi_(y), a sheet resistance of the same level isobtained regardless of the concentration of Pd within the range of Pdconcentration of about 8 atomic % to 30 atomic %.

In accordance with the experimental result shown in FIG. 4 to FIG. 5B,the silicide layer in which Pd is added to NiSi_(y) can have lowelectric resistance, and can obtain a characteristic close to themaximum high-temperature resistance. This characteristic is particularlyapparent when the silicide layer in which Pd is added to NiSi_(y) isformed on SiGe.

Furthermore, regarding the high-temperature resistance of a silicidelayer on a P-type silicon layer, as in a MIS diode that uses P-typesilicon, Pd-added NiSi_(y) shows more satisfactory high-temperatureresistance (higher heat resistance) than Pt-added NiSi_(y). In addition,if the manufacturing cost is compared with the characteristics ofsilicide, Pd-added NiSi_(y) makes it possible to obtain a lower-cost andhigher-performance element (e.g., rectification element) and resistancechange memory that uses this element than Pt-added NiSi_(y).

For example, when the concentration of added Pd is 15 atomic %, Pd-addedNiSi_(y) (Ni_(0.85)Pd_(0.15)Si_(y)) can ensure a relatively low sheetresistance of about 20Ω/□ and have high heat resistance at a temperatureof about 750° C.

As a result, the amount of the addition of the foreign element (D) tosilicide (base material) composed of the Si element (Si) and 3dtransition metal element (M) (the ratio of element D to element M) isparticularly preferably 15 atomic % or less. In this case, the value of“x” in the composition formula of silicide in the present embodiment is0.15 or less.

The relation between the addition of the foreign element to a certainsilicide and crystal grains constituting silicide is described withFIGS. 6A and 6B.

FIG. 6A shows the relation between the concentration [at. %] of anelement added to silicide (denoted by “A” in FIG. 6A) and the crystalgrain diameter [nm] of silicide (denoted by “B” in FIG. 6A), in silicide(NiSi_(y)) included in the resistance change memory according to thepresent embodiment. FIG. 6B shows microscopic images of the surface ofthe silicide layer. FIG. 6B shows the surface of nickel silicide(NiSi_(y)) to which no foreign element is added and the surface ofNiSi_(y) to which 30 atomic % of a foreign element is added.

As shown in FIG. 6A, when the concentration of the foreign element addedto NiSi_(y) is higher, the grain diameter of crystals constituting onesilicide layer is smaller.

Furthermore, as shown in FIG. 6B, one silicide layer is formed ofcrystals having a greater grain diameter in NiSi_(y) to which no foreignelement is added, while one silicide layer is formed of crystals of 30nm or less (hereinafter referred to as microcrystal) in NiSi_(y) towhich foreign element D is added.

As shown in FIG. 6A and FIG. 6B, the grain diameter of crystalsconstituting a certain silicide layer becomes smaller when an elementdifferent in size from the 3d transition metal element forming thesilicide layer, in particular, element D having a greater atomic radiusthan the 3d transition metal element is added.

The smaller crystal leads to a smaller surface area of each crystal andmore stable energy for maintaining crystal. It is considered that suchstabilization of crystal energy attributed to the smaller crystalprevents decomposition of silicide crystals (interatomic bonds) andinhibits agglomeration of a metal and deterioration of the crystal phaseof silicide even if high heat energy is applied to the silicide layer.

As shown in FIG. 4 to FIG. 6B, silicide which includes Si, a 3dtransition metal element forming silicide, and an element having agreater atomic radius than the 3d transition metal element showshigh-temperature resistance (high heat resistance).

A thermal treatment at about 500° C. is used in a back-end process of ageneral semiconductor device (e.g., an integrated circuit). A thermaltreatment at about 600° C. to 700° C. may be used for a resistancechange memory.

The silicide layer included in the resistance change memory according tothe present embodiment is capable of maintaining electric propertieswithout deterioration in the quality of the crystallinity of silicideeven when thermally treated at 700° C. or more.

Therefore, as shown in FIG. 4 to FIG. 6B, silicide which includes a 3dtransition metal element and an element having a greater atomic radiusthan the 3d transition metal element, such as Ni_(1-x)Pd_(x)Si_(y) andNi_(1-x) Pt_(x)Si_(y), has resistance to a higher temperature(hereinafter referred to as high-temperature resistance) than thetemperature of a thermal treatment in a general back-end process, andalso has resistance to a high-temperature thermal treatment used for theresistance change memory.

FIG. 7A and FIG. 7B shows current-voltage characteristics (I-Vcharacteristics) in the junction of silicon and silicide according tothe present embodiment. In FIG. 7A and FIG. 7B, the horizontal axisindicates the voltage applied to a silicon-silicide junction (denoted by“A” in FIG. 7A and FIG. 7B, unit: [V]), and the vertical axis indicatesthe current running through the junction due to the applied voltage(denoted by “B” in FIG. 7A and FIG. 7B, unit: [A]).

FIG. 7A shows I-V characteristics measured under temperature conditionsat 255 K (absolute temperature), 270 K, 285 K and 300 K in the junctionof silicide (Ni_(0.87)Pd_(0.13)Si_(y)) in which the concentration of Pdversus Ni is set at 13 atomic % and P-type silicon. FIG. 7B shows I-Vcharacteristics measured under temperature conditions at 255 K (absolutetemperature), 285 K and 300 K in the junction of silicide(Ni_(0.70)Pd_(0.30)Si_(y)) in which the concentration of Pd versus Ni isset at 30 atomic % and P-type silicon. In addition, “y” is a valueindicated by a range of 0<y≦2.

As shown in FIG. 7A, the junction of Ni_(0.87)Pd_(0.13)Si_(y) and P-typesilicon forms a Schottky junction. From the temperature dependence ofeach I-V characteristic shown in FIG. 7A, the height of a Schottkybarrier of this junction measures about 0.28 eV.

As in FIG. 7A, Ni_(0.70)Pd_(0.30)Si_(y) and P-type silicon forms aSchottky junction. From the temperature dependence of each I-Vcharacteristic shown in FIG. 7B, the height of a Schottky barrier ofNi_(0.70)Pd_(0.30)Si_(y) and P-type silicon measures about 0.31 eV.

Generally, in a Schottky junction of P-type silicon and each of NiSi_(y)to which no Pd is added, titanium silicide (TiSi_(y)) and tantalumsilicide (TaSi_(y)), the height of a Schottky barrier is about 0.4 eV to0.5 eV.

The following is shown from the result of measurements in FIG. 7A andFIG. 7B.

If element D having a greater atomic radius than the atomic radius ofelement (3d transition metal element) M is added to silicide indicatedby “MSi_(y)”, the work function of silicide can be modulated. As shownin FIG. 7A and FIG. 7B, the modulation of the work function of silicidedepends on the concentration of added element D.

Furthermore, if the work function of silicide is modulated by theaddition of a foreign element, the work function of silicide versussilicon can be optimized, and the interface resistance of thesilicon-silicide junction can be reduced.

For example, as described above, the Schottky barrier against P-typesilicon is lower in NiSi_(y) to which Pd is added than in NiSi_(y) towhich no Pd is added. That is, the interface resistance against P-typesilicon can be lower in NiSi_(y) to which Pd is added than in NiSi_(y),TiSi_(y) and TaSi_(Y) to which no foreign element is added.

The addition of the foreign element (e.g., Pt or Pd) to silicide tendsto cause the segregation of Pt or Pd or of other impurities contained insilicon at the interface between silicide and silicon. Thus, a layer inwhich impurities are segregated with high concentration (referred to asa high-concentration segregation layer) is formed at thesilicide-silicon interface. As a result, the interface resistance of thesilicon-silicide junction is reduced.

As shown in FIG. 7A and FIG. 7B, in silicide including a 3d transitionmetal element and a foreign element (additional element) having agreater atomic radius than the atomic radius of the 3d transition metalelement, the work function of silicide can be modulated by the additionof the foreign element, so that the interface resistance of thesilicon-silicide junction can be reduced.

In addition, Pd or Pt is added to NiSi_(y) in the case mainlyillustrated in FIG. 4 to FIG. 7B, and the characteristics of silicideincluded in the resistance change memory according to the presentembodiment have been described. However, substantially the same tendencyas that in FIG. 4 to FIG. 7B is also shown and similar results can beobtained in the present embodiment when silicide made of an Si elementand a different 3d transition metal element (e.g., Ti) and otheradditional elements (foreign elements) are used.

Advantages in the following case are described with FIG. 8A and FIG. 8B:the silicide layer (M_(1-x)D_(x)Si_(y)) including the Si element 50, the3d transition metal element 51, and at least one kind of the element 52having atomic radius r2 greater than atomic radius r1 of the 3dtransition metal element 51 is applied to the resistance change memory,as shown in FIG. 3.

FIG. 8A is a diagram schematically showing the state of the non-ohmicelement included in the resistance change memory when subjected to ahigh-temperature thermal treatment. In FIG. 8A, diodes 30X, 30constituting a cell unit of the cross-point type resistance changememory are shown. In addition, PIN diodes constituted of threesemiconductor layers (silicon layers) 31, 32, 33 are shown as examplesof diodes 30X, 30 in FIG. 8A.

Here, the PIN diode has a stack structure composed of the intrinsicsemiconductor layer 32, semiconductor layer 33 containing a large amountof a P-type impurity (having a high concentration of acceptorimpurities), and the semiconductor layer 31 containing a large amount ofan N-type impurity (a high concentration of donor impurities). Inaddition, the stack positions (vertical relation) of the P-typesemiconductor layer 33 and the N-type semiconductor layer 31 may bereverse to that in FIG. 8A.

In FIG. 8A, a silicide (MSi_(y)) 90 to which no foreign element is addedis provided on one end (semiconductor layer 33 side) of the diode 30X.In FIG. 8A, a silicide (M_(1-x)D_(x)Si_(y)) 39 to which foreign elementD is added is provided on one end (semiconductor layer 33 side) of thediode 30.

In the process of manufacturing the resistance change memory, ahigh-temperature thermal treatment at about 600° C. to 800° C. may beconducted to form the non-ohmic element and the memory element.

For example, the high-temperature resistance (heat resistance) ofNiSi_(y) to which no foreign element is added is about 600° C. When athermal treatment at a high temperature of 600° C. or more is conducted,agglomerates 59 of metal element M forming silicide may be formed in thesemiconductor layer 33 where the silicide layer 90 is provided and inthe intrinsic semiconductor 32 thereunder, in the diode 30X that usessilicide to which no foreign element is added (M_(x)Si_(y)), as shown inFIG. 8A.

Furthermore, transition metal element (transition metal atom) M candiffuse into semiconductor layers 33, 32 due to the high-temperaturethermal treatment. In particular, the intrinsic semiconductor 32 isprovided between the N-type semiconductor layer 31 and the P-typesemiconductor layer 33 in the PIN diode. Therefore, the diffusion of themetal atoms in the intrinsic semiconductor 32 forms an impurity level inthe intrinsic semiconductor 32 and significantly deteriorates theelectric properties of the PIN diode.

Moreover, due to an excessive silicide reaction resulting from thehigh-temperature thermal treatment, the silicide layer 91 may be formedto erode not only the end of the semiconductor layer 33 but also regionswhere formation of no silicide layer is needed, such as the inside ofthe semiconductor layer 33 and the intrinsic semiconductor 32. Thiserosion may break down a silicon-silicon junction.

This deteriorates the electric characteristics of the diode 30X, anddegrades the operating characteristics of the resistance change memory.Moreover, if the thickness of semiconductor layer 33 is increased toreduce adverse effects of the agglomeration/diffusion of the metalelement and the erosion by silicide, shrinking (decrease of the aspectratio) of the cell unit is difficult.

Moreover, since the agglomeration/diffusion of the metal element and theerosion of the semiconductor layer by the silicide layer are nonuniformin the memory cell array, characteristic variation among the cell unitsin the memory cell array increases.

On the other hand, the silicide layer 39 including the Si element, the3d transition metal element (M) and the element (D) having an atomicradius greater than the atomic radius of the 3d transition metal elementhas high-temperature resistance ranging from 700° C. to 750° C. owing tothe smaller crystal grain as described with FIG. 4 to FIG. 6B.

Therefore, as shown in FIG. 8A, in diode 30 having silicide layer 39,the agglomeration/diffusion of the metal element (M or D) and theerosion by silicide are inhibited by the high heat resistance ofsilicide (M_(1-x)D_(x)Si_(y)) even if a thermal treatment at 500° C. ormore is conducted.

This reduces the deterioration of the characteristics of the cell unitincluding the silicide layer, for example, the forward biascharacteristic and reverse bias characteristic of the diode due to thehigh-temperature thermal treatment included in the process ofmanufacturing the resistance change memory.

FIG. 8B shows one example of the I-V characteristic of the diode. InFIG. 8B, the horizontal axis indicates a potential difference appliedacross both ends of the diode (denoted by “D” in FIG. 8B, unit: [V]),and the vertical axis indicates, on a logarithmic scale, the currentrunning through the junction due to the applied potential difference(denoted by “E” in FIG. 8B, unit: [A]).

In FIG. 8B, characteristic line (full line) A indicates a simulationresult obtained by a self-manufactured simulator regarding the I-Vcharacteristic of the diode which is provided, on one end, with thesilicide layer 39 including the Si element, the 3d transition metalelement (M) and the additional element (D) as in, for example, the diode30 shown in FIG. 8A. Characteristic line (chain line) B indicates asimulation result regarding the I-V characteristic of the diode which isprovided, on one end, with the silicide layer including the Si elementand the 3d transition metal element (M), that is, the silicide layer towhich no foreign element is added. A silicon-silicide interfaceresistance model is applied to the simulations indicated by thesecharacteristic lines A, B.

Characteristic line (broken line) C indicates measurements of the I-Vcharacteristic of the diode shown by characteristic line B.Characteristic line B and characteristic line C show that the simulationand the measurements substantially correspond to each other.

In addition, the silicide layer forms an interface with the P-typesilicon layer in the simulation and experiment shown in FIG. 8B.Moreover, in the diode corresponding to each of characteristic lines A,B, C, the silicide layer includes the same kind of 3d transition metalelement.

The intensity (upper limit value) of an output current (referred to as aforward current) of the rectification element when a forward bias isapplied is subject to the intensity of the interface resistance of thesilicon-silicide junction. Specifically, the upper limit value of theforward current decreases if the interface resistance increases.

As shown in FIG. 7A and FIG. 7B, the work function of silicide can bemodulated by the addition of an additional element (foreign element) ofdesired concentration to silicide. Thus, at the junction of silicon andsilicide, resistance (interface resistance) generated in the interfacecan be reduced. That is, the interface resistance can be reduced, sothat a current loss resulting from the interface resistance can bereduced.

Consequently, as indicated by characteristic line A in FIG. 8B, theupper limit of the forward current of the rectification element when aforward bias is applied can be improved in the resistance change memoryaccording to the present embodiment, as compared with the rectificationelement that uses silicide indicated by characteristic line B to whichno foreign element is added.

Therefore, at a certain voltage applied to the rectification element(non-ohmic element), the rectification element can supply a higherforward current to the memory element. This also contributes to areduction in the power consumption of the resistance change memory.

Furthermore, since the silicide layer to which a foreign element isadded has high-temperature resistance in the resistance change memoryaccording to the present embodiment as described above, theagglomeration and diffusion of the metal element included in thesilicide layer and the erosion of other parts by the silicide layer canbe inhibited. This makes it possible to prevent the formation of animpurity level in the semiconductor layer and the breakdown of thejunction.

Thus, in the resistance change memory according to the presentembodiment, a high breakdown voltage can be ensured in the rectificationelement used as the non-ohmic element, and an output current (referredto as a reverse current) of the rectification element when a reversebias is applied can be reduced.

Furthermore, in the resistance change memory according to the presentembodiment, since the formation of randomly generated agglomerates andthe diffusion of the metal element in the silicon layer can beinhibited, characteristic variation of the cell units in one memory cellarray can be reduced.

Moreover, the forward bias/reverse bias characteristics of therectification element can be improved, which contributes to thethickness reduction of the layers constituting the rectification elementand the reduction of the area of the cell unit.

Consequently, according to the resistance change memory in theembodiment of the present invention, characteristic deterioration of theresistance change memory can be inhibited.

Example

(1) Configuration

An example of the resistance change memory according to the embodimentof the present invention is more specifically described with FIG. 9 toFIG. 19.

(a) Configurations of the Memory Cell Array and the Control Circuit

FIG. 9 specifically shows one example of the configurations of theinterconnect lines and the cell units in the cross-point type memorycell array.

Here, cell units CU1, CU2 in two memory cell arrays M1, M2 in FIG. 2 areshown. In this case, the cell units in two memory cell arrays M3, M4 inFIG. 2 are the same in configuration as the cell units in two memorycell arrays M1, M2 in FIG. 2.

Each of cell units CU1, CU2 is composed of a memory element and anon-ohmic element that are connected in series. Here, a rectificationelement is used for the non-ohmic element.

There are various patterns of the connection between the memory elementand the rectification element. However, all the cell units in one memorycell array need to be the same in the connection between the memoryelement and the rectification element.

FIG. 10 shows the connection between the memory element and therectification element.

In one cell unit, there are a total of four patterns of the connectionbetween the memory element and the rectification element; two patternsof the positional relation between the memory element and therectification element, and two patterns of the direction of therectification element. Therefore, there are sixteen patterns (fourpatterns x four patterns) of the connection between the memory elementand the rectification element regarding the cell units in two memorycell arrays.

a to p of FIG. 10 denote sixteen patterns of connection.

While the embodiment is applicable to all of the sixteen patterns ofconnection, the connection of “a” of FIG. 10 is mainly described belowby way of example.

FIG. 11A and FIG. 11B show a first example of the layout of the firstand second control circuits.

Memory cell array Ms in FIG. 11A corresponds to one layer M1, M2, M3, M4of cross-point type memory cell array 2 shown in FIG. 2. As shown inFIG. 11A, memory cell array Ms is composed of a plurality of arrayedcell units CUs. The cell units CUs are connected on one end tointerconnect lines Ls (j−1), Ls (j), Ls (j+1), and connected on theother end to interconnect lines Ls+1 (i−1), Ls+1 (i), Ls+1 (i+1).

As shown in FIG. 11B, memory cell array Ms+1 is composed of a pluralityof arrayed cell units CUs+1. The cell units CUs+1 are connected on oneend to interconnect lines Ls+1 (i−1), Ls+1 (i), Ls+1 (i+1), andconnected on the other end to interconnect lines Ls+2 (j−1), Ls+2 (j),Ls+2 (j+1).

Here, s is 1, 3, 5, 7, . . .

The first control circuit 3 is connected to interconnect lines Ls+1(i−1), Ls+1 (i), Ls+1 (i+1) on one end in the first direction via switchelements SW1. Switch elements SW1 are controlled by, for example,control signals φs+1 (i−1), φs+1 (i), φs+1 (i+1). The switch element SW1is configured by, for example, an N-channel field effect transistor(FET).

The second control circuit 4 is connected to interconnect lines Ls(j−1), Ls (j), Ls (j+1) on one end in the second direction via switchelements SW2. Switch elements SW2 are controlled by, for example,control signals φs (j−1), φs (j), φs (j+1). The switch element SW2 isconfigured by, for example, an N-channel FET.

Second control circuit 4 is connected to interconnect lines Ls+2 (j−1),Ls+2 (j), Ls+2 (j+1) on one end in the second direction via switchelements SW2′. Switch elements SW2′ are controlled by, for example,control signals φs+2 (j−1), φs+2 (j), φs+2 (j+1). Switch element SW2′ isconfigured by, for example, an N-channel field effect transistor.

FIG. 11C shows a second example of the layout of the first and secondcontrol circuits. In addition, in FIG. 11C, the internal configurationof memory cell arrays Ms, Ms+1, Ms+2, Ms+3 is substantially the same asthat of the memory cell array shown in FIG. 11A or FIG. 11B and istherefore not shown.

The layout in the second example is different from the layout in thefirst example in that first control circuits 3 are disposed at both endsof the first direction of memory cell array Ms, Ms+1, Ms+2, Ms+3 and inthat second control circuits 4 are disposed at both ends of the seconddirection of memory cell array Ms, Ms+1, Ms+2, Ms+3.

Here, s is 1, 5, 9, 13, . . .

First control circuits 3 are connected to interconnect lines Ls+1 (i−1),Ls+1 (i), Ls+1 (i+1) on both ends in the first direction via switchelements SW1. Switch elements SW1 are controlled by, for example,control signals φs+1 (i−1), φs+1 (i), φs+1 (i+1), φs+3 (i−1), φs+3 (i),φs+3 (i+1). The switch element SW1 is configured by, for example, anN-channel field effect transistor.

Second control circuits 4 are connected to interconnect lines Ls (j−1),Ls (j), Ls (j+1) on both ends in the second direction via switchelements SW2. Switch elements SW2 are controlled by, for example,control signals φs (j−1), φs (j), φs (j+1), φs+2 (j−1), φs+2 (j), φs+2(j+1). The switch element SW2 is configured by, for example, anN-channel field effect transistor.

(b) Configuration of the Cell Unit

FIG. 12A to FIG. 12F show examples of the configuration of the cellunit.

One cell unit CU is disposed between two interconnect lines 60, 65. Onecell unit CU is composed of one memory element 20 and one non-ohmicelement 30.

In one cell unit, the memory element 20 is stacked on the non-ohmicelement 30, or the non-ohmic element 30 is stacked on the memory element20.

Here, in the stacking direction of two elements 20, 30, an interconnectline 65 side is called an upper side (upper end or upper part), and aninterconnect line 60 side is called a lower side (lower end or lowerpart).

Here, a PIN diode is illustrated as the non-ohmic element 30. Asdescribed above, the PIN diode has a structure in which an intrinsicsemiconductor layer is interposed between a P-type semiconductor layerand an N-type semiconductor layer. In addition, in accordance with theconnection of two cell units of the memory cell array 2 shown in FIG.10, the vertical relation between an anode layer and a cathode layer ofthe diode 30 in the stacking direction may be reverse.

For example, in the cell unit CU shown in FIG. 12A, in case the uppersemiconductor layer 33 is a P-type semiconductor layer (anode layer) ofthe PIN diode, the lower semiconductor layer 31 is an N-typesemiconductor layer (cathode layer) of the PIN diode. On the contrary,in case the upper semiconductor layer 33 is an N-type semiconductorlayer (cathode layer) of the PIN diode, the lower semiconductor layer 31is a P-type semiconductor layer (anode layer) of the PIN diode. In eachcase, the semiconductor layer 32 between two semiconductor layers 31, 33is an intrinsic semiconductor layer of the PIN diode.

In the cell unit in FIG. 12B to FIG. 12F as well, two semiconductorlayers 31, 33 sandwiching the intrinsic semiconductor layer 32 have asimilar relation to that in FIG. 12A when a PIN diode is used for therectification element (non-ohmic element) 30.

Each of semiconductor layers 31, 32, 33 is made of a material containingsilicon as the main component. For example, silicon carbide (SiC),silicon germanium (SiGe), silicon tin (SiSn), polycrystalline silicon(Poly-Si), amorphous silicon or monocrystalline silicon is used to formsemiconductor layers 31, 32, 33. In SiC, the concentration of C (carbon)against Si is about 0 to 3 atomic %. In SiGe, the concentration of Ge(germanium) versus Si is about 0 to 30 atomic %. In SiSn, theconcentration of Sn (tin) versus Si is about 0 to 3 atomic %.

Furthermore, boron (B) is added to semiconductor layers 31, 33containing P-conductivity-type silicon as the main component. Phosphorus(P) or arsenic (As) is added to semiconductor layers 31, 33 containingN-conductivity-type silicon as the main component. In addition, theintrinsic semiconductor layer may contain P-type/N-type impurities, butthe concentration of the P-type/N-type impurities contained in theintrinsic semiconductor layer 32 is lower than the concentration ofimpurities contained in semiconductor layers 31, 33.

The memory element 20 has a structure in which the resistance changefilm 21 is interposed between two electrodes 25, 26. In the examplesshown in FIG. 12A to FIG. 12F, the electrode 25 on the lower side in thestacking direction of two elements 20, 30 is called a lower electrode,and the electrode 26 on the upper side is called an upper electrode.

The resistance change film 21 is a layer made of a material with aresistance value that changes upon application of, for example, avoltage, a current or heat, or a material having a physicality such as aresistance value or capacitance (impedance) that changes due to a phasechange. The resistance value of the resistance change film 21 isreversibly changed by the application of energy such as a voltage, andthe condition in which the resistance value has changed is retained in anonvolatile manner until energy that changes the resistance value isagain provided.

In addition, the memory element 20 may be an element that shows suchcharacteristics by the combination of electrodes 25, 26 and theresistance change film 21, or the resistance change film 21 may be anelement that shows such characteristics.

Interconnect lines 60, 65 are used as a bit line and a word line, asdescribed above. Interconnect lines 60, 65 are made of, for example, ametal such as Cu, Al or W, a metal compound such as titanium nitride(TiN) or tungsten nitride (WN), or silicide such as NiSi or TiSi_(y).

In the example shown in FIG. 12A, the memory element 20 is stacked onthe diode 30. The diode 30 is disposed on the interconnect line 60. Oneend (bottom) of the diode 30 is electrically connected to theinterconnect line 60. The other end (top) of the diode 30 iselectrically connected to one end (lower electrode) of the memoryelement 20. The other end (upper electrode) of the memory element 20 iselectrically connected to the interconnect line 65.

The diode 30 has the silicide layer 39A on its upper end, and thesilicide layer 39A is provided on the top of the upper semiconductorlayer 33. The silicide layer 39A intervenes between the semiconductorlayer 33 and the lower electrode 25 of the memory element 20. Forexample, the silicide layer 39A is in direct contact with the lowerelectrode 25.

Furthermore, in the example shown in FIG. 12B, the diode 30 is stackedon memory element 20. In this case, the memory element 20 is disposed onthe interconnect line 60. One end (lower electrode) of memory element 20is electrically connected to the interconnect line 60. The other end(upper electrode) of the memory element 20 is electrically connected toone end (bottom) of the diode 30. The other end (top) of the diode 30 iselectrically connected to the interconnect line 65. In the cell unitshown in FIG. 12B, the diode 30 has the silicide layer 39B on its lowerend, and the silicide layer 39B is provided on the bottom of the lowersemiconductor layer 31. Silicide layer 39B intervenes between thesemiconductor layer 31 and the upper electrode 26. For example, thesilicide layer 39B is in direct contact with the upper electrode 26.

In the example shown in FIG. 12C, the memory element 20 is stacked onthe diode 30. The silicide layer 39B is provided on the bottom of thesemiconductor layer 31 of the diode 30. The silicide layer 39Bintervenes between the semiconductor layer 31 and the interconnect line60. For example, the silicide layer 39B is in direct contact with theinterconnect line 60.

In the example shown in FIG. 12D, the diode 30 is stacked on the memoryelement 20. The silicide layer 39A is provided on the top of thesemiconductor layer 33 of the diode 30. The silicide layer 39Aintervenes between the semiconductor layer 33 and the interconnect line65. For example, the silicide layer 39A is in direct contact with theinterconnect line 65.

As shown in FIG. 12A to FIG. 12D, the silicide layer 39A, 39B is onlyformed on a single end (one end) of the diode, so that the process ofmanufacturing the diode having the silicide layer 39A, 39B can besimpler.

Especially, when a silicide in which a metal element having a workfunction close to that of a valence band such as Pt, Pd, Os, Ir, Rh orRu is added to a 3d transition metal element such as Ni or Ti that isused in the present embodiment is used as silicide (M_(1-x)D_(x)Si_(y))in the present embodiment, the formation of the silicide layer 39A, 39Bin a semiconductor layer containing P-conductivity-type silicon as themain component is effective. The reason for this is as follows: Thesystem to which, for example, the above-mentioned Pt belongs has a workfunction (a Fermi level) close to that of the valence band of P-type Si,and such elements can improve the segregation of impurities at theinterface and the activation rate of impurities. Therefore, theformation of an electric junction of silicide that uses theabove-mentioned system and a P-type semiconductor (e.g., P-type Si) ispreferable as regards the electric properties of the element.

Furthermore, as shown in FIG. 12E and FIG. 12F, silicide layers 39A, 39Bmay be provided on both ends (top/bottom) of the diode 30, respectively.

In the example shown in FIG. 12E, silicide layer 39A provided at the topof the diode 30 intervenes between the lower electrode 25 and thesemiconductor layer 33. Moreover, the silicide layer 39B provided at thebottom of the diode 30 intervenes between the semiconductor layer 31 andthe interconnect line 60. For example, the silicide layer 39A on theupper side of the element is in direct contact with the lower electrode25, and the silicide layer 39B on the bottom side of element is indirect contact with the interconnect line 60.

In the example shown in FIG. 12F, the silicide layer 39A provided at thetop of the diode 30 intervenes between the semiconductor layer 33 andthe interconnect line 65. Moreover, the silicide layer 39B provided atthe bottom of the diode 30 intervenes between the semiconductor layer 31and the upper electrode 26. For example, the silicide layer 39A on theupper side of the element is in direct contact with the interconnectline 65, and the silicide layer 39B on the bottom side of the element isin direct contact with the upper electrode 26.

One of the cell units shown in FIGS. 12A and 12F is disposed between thebit line and the word line to satisfy the connection relation shown inFIG. 10 to configure a memory cell array and a cross-point type memorycell array.

As in the cell units CU shown in FIG. 12A to FIG. 12F, the silicidelayer 39A, 39B is provided on at least one end (top) or the other end(bottom) of the non-ohmic element (e.g., rectification element). Asshown in FIG. 3, the silicide layer 39A, 39B includes the Si element 50,the 3d transition metal element 51 that combines with the Si element toform silicide, and the additional element (foreign element) 52 having anatomic radius greater than the atomic radius of the 3d transition metalelement.

The junction of the silicide layer 39A, 39B and the silicon layer 31, 32may have a segregation layer (not shown) in which impurities(donor/acceptor) contained in the silicon layer are segregated with highconcentration due to the addition of the additional element 52.

Further, the silicide layer 39A, 39B may contain one kind of additionalelement, or may contain two or more kinds of additional elements.

Although three semiconductor layers are stacked as in a PIN diode in thestructures illustrated in FIG. 12A to FIG. 12F, ametal-insulator-semiconductor (MIS) diode, a SIS structure or a MIMstructure may be used for the non-ohmic element 30, or a structure inwhich two layers are stacked as in a PN diode may be used for thenon-ohmic element. Moreover, the non-ohmic element may be an elementwhich allows non-ohmic characteristics to be formed by four layers(films).

For example, if the non-ohmic element 30 having the silicide layer 39Ain the present embodiment is a MIS diode, three layers are stacked inthe following order: a metal layer, an insulating layer and asemiconductor layer from the lower side; or a semiconductor layer, aninsulating layer and a metal layer from the lower side. In addition, astructure in which the silicide layer is only provided on thesemiconductor layer is sufficient for the MIS diode. However, thesemiconductor layer and the silicide layer may be provided on thesurface of the metal layer opposite to the junction surface of the metallayer and the insulating layer.

Moreover, the non-ohmic element 30 may have a structure in which threeor more P-type semiconductor layers and N-type semiconductor layers arealternately stacked, such as a three-layer bipolar transistor typestructure or a four-layer thyristor type structure. Especially, in casethe upper semiconductor layer 33 is a P-type semiconductor layer or anN-type semiconductor layer in the above-mentioned structure, thesilicide layer 39A, 39B described in the present embodiment may beprovided in the semiconductor layer 33.

In FIG. 12A to FIG. 12F, a diffusion preventing layer or an adhesivelayer may be provided between the interconnect line 60, 65 and thenon-ohmic element 30, between the non-ohmic element 30 and the memoryelement 20 or between the memory element 20 and the interconnect line60, 65. The diffusion preventing layer prevents the diffusion ofconstituent atoms or constituent elements of each part between partsthat are joined together. The adhesive layer secures the bonding forcebetween joined parts and prevents the separation of the parts. Inaddition, electrodes 25, 26 may have substantially the same function asthe diffusion preventing layer or the adhesive layer.

FIG. 13A to FIG. 13C show one example of the non-ohmic element (here,the rectification element) and the work function of silicide.

In FIG. 13A and FIG. 13B, a PIN diode is shown as the non-ohmic element.In case the non-ohmic element includes a semiconductor layer as in thePIN diode, the silicide layer 39 used in the present embodiment isprovided in the P-type semiconductor layer 35 or the N-typesemiconductor layer 37 depending on the connection of the cell units.The intrinsic semiconductor layer 36 is provided between the P-typesemiconductor layer 35 and the N-type semiconductor layer 37.Semiconductor layers 35, 36, 37 are semiconductor layers containingsilicon as the main component, and may be a layer containing Ge or C inaddition to silicon. Here, for ease of explanation, these semiconductorlayers are simply referred to as P-type/N-type silicon layers.

When the silicide layer and the N-type silicon layer form an interface(junction), the relation between the conduction band of the N-typesilicon layer and the work function of the silicide layer affects theelectric properties of the element. When the silicide layer and theP-type silicon layer form an interface (junction), the relation betweenthe valence band of the P-type silicon layer and the work function ofthe silicide layer affects the electric properties of the element. Thatis, the difference between the conduction band (N-type Si)/valence band(P-type Si) of silicon and the work function of silicide is one of thecauses of interface resistance.

In case the energy difference between the conduction band (N-typeSi)/valence band (P-type Si) of silicon and the work function ofsilicide is closer to 0 eV, the interface resistance is lower, and acurrent and a voltage output via the silicon-silicide junction arehigher.

As long as the P-type/N-type silicon layer that forms an interface withthe silicide layer is a P+/N+ silicon layer having a high impurityconcentration of, for example, 10²⁰/cm³ or more, an energy differencethat can reduce a loss caused by the interface resistance is sufficient.In this case, the energy difference between the valence band of P-typesilicon and the work function of silicide and the energy differencebetween the conduction band of N-type silicon and the work function ofsilicide may be, by way of example, 0.7 eV or less.

As described with FIG. 7A and FIG. 7B, the magnitude of the workfunction of silicide to silicon can be adjusted by adding at least onekind of additional element having an atomic radius greater than theatomic radius of the 3d transition metal element to the silicide layercomposed of the Si element and the 3d transition metal element.

Therefore, by controlling the combination of the material of silicideand an additional element and controlling the addition amount of theadditional element, the work function of silicide can be adjusted to avalue suitable for silicon forming the rectification element. This makesit possible to reduce the interface resistance generated at the junctionof P-type/N-type semiconductor (e.g., P-type/N-type silicon) andsilicide.

FIG. 13C shows the magnitude of the work function of each kind ofsilicide. In FIG. 13C, the horizontal axis indicates a base material forforming silicide layer 39 of the present embodiment, and the verticalaxis indicates the work function to silicon (denoted by “A” in FIG. 13C,unit: [eV]).

As shown in FIG. 13A, when an interface is formed between silicide layer39 and the P-type semiconductor layer (e.g., the P-type silicon layer),silicide belonging to group G1 enclosed by a full line in FIG. 13C ispreferably used as the base material (also referred to as a basesilicide material) for forming silicide layer 39 in the P-type siliconlayer.

Among silicides in group G1, TiSi_(y), VSi_(y), CrSi_(y), MnSi_(y),FeSi_(y), CoSi_(y), NiSi_(y), NdSi_(y), MoSi_(y), HfSi_(y), TaSi_(y),WSi_(y), PdSi_(y), IrSi_(y), PtSi_(y), RhSi_(y), ReSi_(y) or OsSi_(y) isused as the base silicide material for the silicide layer 39. It ispreferable to add a foreign element to these silicides in order toreduce the resistance of the interface between the silicide layer 39 andthe P-type silicon layer. In addition, “y” in each composition formulais indicated by a value higher than 0 and a value equal to or lower than2.

As shown in FIG. 13B, when an interface is formed between silicide layer39 and the N-type semiconductor layer (e.g., the N-type silicon layer),silicide belonging to group G2 enclosed by a broken line in FIG. 13C ispreferably used as the base silicide material for forming the silicidelayer 39 in the N-type silicon layer.

Among silicides in group G2, TiSi_(y), VSi_(y), CrSi_(y), MnSi_(y),FeSi_(y), CoSi_(y), NiSi_(y), NdSi_(y), MoSi_(y), HfSi_(y), TaSi_(y),YSi_(y), YbSi_(y), ErSi_(y), HoSi_(y), DySi_(y), GdSi_(y) or TbSi_(y) isused as the base silicide material for the silicide layer 39. It ispreferable to add a foreign element to these silicides in order toreduce the resistance of the interface between the silicide layer 39 andthe N-type silicon layer. In addition, “y” in each composition formulais a value indicated by 1 to 2.

Not only the amount of doping of the silicide layer 39 with theadditional element adjusted but also the material of silicide to serveas the base silicide material for the silicide layer 39 is changeddepending on whether the silicon layer that combines with the silicidelayer to form a junction is a P-type silicon layer or an N-type siliconlayer. Thereby, the high-temperature resistance of silicide layer 39 isimproved, and the resistance of the interface between the silicon layerand silicide layer 39 can be reduced by using a material having moresuitable physicality.

In addition, from the perspective of the high-temperature resistance,TiSi_(y), CoSi_(y), PtSi_(y), TaSi_(y) or WSi_(y) is effective as thebase material for forming silicide layer 39 to which a foreign elementis added. Moreover, in the case illustrated in FIG. 13A and

FIG. 13B, the silicide layer 39 forms an interface with theP-type/N-type silicon layer that configures the PIN diode. However, theexample shown in FIG. 13A and FIG. 13B is substantially the same as thecase where the silicide layer 39 is provided in a P-type/N-type siliconlayer that configures a different element structure, such as a PINstructure, a MIS structure (e.g., a MIS diode) or a PN structure (e.g.,a PN diode).

The high-temperature resistance of the silicide layer can be improvedand the interface resistance can be reduced by adjusting thearrangement, in the cell unit, of the silicide layer 39, 39A, 39B whichincludes an additional element having a greater atomic radius than theatomic radius of the 3d transition metal element or by adjusting thematerial serving as the base material for the silicide layer 39, 39A,39B as shown in FIG. 12A to FIG. 13C in accordance with theconfigurations of the memory cell array and the cell unit.

In the resistance change memory according to the present embodiment, thehigh-temperature resistance of the silicide layer is improved by theaddition of the foreign element, so that the agglomeration or diffusionof the metal elements (atoms) included in the silicide layer and theerosion by the silicide layer can be inhibited. As a result, thebreakdown voltage of the rectification element can be higher, and theoutput current of the rectification element when a reverse bias isapplied can be reduced.

Furthermore, in the resistance change memory according to the presentembodiment, the interface resistance of the silicon-silicide junction isreduced by the addition of the foreign element, so that the outputcurrent of the rectification element when a forward bias is applied canbe increased.

Moreover, these improvements in the element characteristics cancontribute to the thickness reduction of the element and the reductionof a cell area. As described above, according to the resistance changememory in the embodiment, characteristic deterioration of the elementused in the resistance change memory can be inhibited.

(2) Manufacturing Method

(a) First Manufacturing Method

A first method of manufacturing the resistance change memory accordingto the present embodiment is described with FIG. 14A to FIG. 14G. Here,FIG. 14A to FIG. 14E show sectional process views taken along the seconddirection of a memory cell array in one step of the presentmanufacturing method. Further, FIG. 14F and FIG. 14G show sectionalprocess views taken along the first direction of a memory cell array inone step of the present manufacturing method.

Although a memory element is stacked on a non-ohmic element in thestructure of a cell unit formed in the case of this manufacturingmethod, this manufacturing method is not limited to this structure.

As shown in FIG. 14A, a conductive layer 60X serving as a interconnectline is deposited on the substrate (e.g., an interlayer insulating film)11 by, for example, a chemical vapor deposition (CVD) method or asputter method.

A plurality of layers for forming a rectification element (non-ohmicelement) of a cell unit are sequentially deposited on the conductivelayer 60X by, for example, the chemical vapor deposition (CVD) method.

For example, in case the rectification element is a PIN diode, threesemiconductor layers 31X, 32X, 33X are stacked. Semiconductor layers31X, 32X, 33X contain silicon, and are made of, for example, at leastone of an SiC layer, an SiGe layer, an SiSn layer, a polycrystalline Silayer, an amorphous silicon layer and a monocrystalline Si layer. In theSiC layer, the ratio of C to Si is, for example, 0 atomic % to 3 atomic%. In the SiSn layer, the ratio of Sn to Si is, for example, 0 atomic %to 3 atomic %. In the SiGe layer, the ratio of Ge to Si is, for example,0 atomic % to 30 atomic %.

In case that the rectification element in the cell unit is a PIN diode,one of semiconductor layers 31X, 33X is a P-type semiconductor layer(e.g., B-doped Si), and the other is an N-type semiconductor layer(e.g., P-doped Si). The semiconductor layer 32X between thesemiconductor layer 31X and the semiconductor layer 33X is an intrinsicsemiconductor layer.

In case a PN diode is used as the rectification element, twosemiconductor layers are stacked on the conductive layer 60X. In case aMIS diode is used as the rectification element, a metal layer, aninsulating layer and a semiconductor layer are stacked on the conductivelayer 60X.

The stacking order of two or more layers such as the semiconductorlayers constituting the rectification element is appropriately changeddepending on which of the circuit configurations, indicated by a to p ofFIG. 10, the cell unit has. For example, when the cell unit has theconfiguration indicated by “a” of FIG. 10, the N-type semiconductorlayer (cathode layer) 31X having a thickness of about 5 nm to 30 nm isdeposited on the conductive layer 60X in FIG. 14A. The intrinsicsemiconductor layer (I layer) 32X having a thickness of about 50 nm to120 nm is deposited on the N-type semiconductor layer 31X. Further, theP-type semiconductor layer (e.g., an anode layer) 33X having a thicknessof about 5 nm to 30 nm is deposited on the intrinsic semiconductor layer32X.

Here, three stacked layers (semiconductor layers) 31X, 32X, 33X arereferred to as silicon layers 31X, 32X, 33X.

In addition, a diffusion preventing layer, an adhesive layer and ahigh-concentration impurity layer may be formed between the conductivelayer 60X and the silicon layer 31X.

A metal film 59 is deposited on the semiconductor layer 33X by, forexample, the sputter method or the CVD method. In the firstmanufacturing method according to the present embodiment, the metal film59 is an alloy film. This alloy film includes a 3d transition metalelement 51, and an additional element 52 having an atomic radius greaterthan the atomic radius of the 3d transition metal element 51.

The 3d transition metal element 51 is one kind of element selected fromthe above-mentioned 3d transition metal element group consisting of Sc,Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn. The additional element 52 is atleast one kind of element selected from the above-mentioned additionalelement group consisting of Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La,Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re,Os, Ir, Pt, Au, In, Ti, Ge, Sn and Pb.

For example, when Ni or Ti is used as the 3d transition metal element51, Pd or Pt is used as the additional element 52. In addition, themetal film 59 may include two or more kinds of additional elements. Forexample, the metal film 59 may include both Pd and Pt.

The substrate 11 is performed to a thermal treatment (silicidetreatment) for forming a silicide layer. For example, the silicon layer33 serves as the source of silicon (hereinafter referred to as a baselayer) for forming a silicide layer. The thermal treatment is conductedat a temperature ranging from, for example, 500° C. to 800° C. A rapidthermal annealing (RTA) method or other heating method may be used as aheating method for the silicide treatment.

A silicide reaction between the silicon layer 33X and the alloy film 59is caused by this thermal treatment. Therefore, as shown in FIG. 14B,the silicide layer 39X is formed on the top of silicon layer 33X. Thesilicide layer 39X includes the Si element 50 derived from the siliconlayer 33X, the 3d transition metal element 51 derived from the alloyfilm, and the additional element 52. Crystal grains constitutingsilicide layer 39X are rendered microcrystal by the addition of aforeign element to a certain silicide.

In FIG. 14A, the ratio of the 3d transition metal element 51 and theadditional element 52 included in the alloy film 59 is appropriately seton the basis of the stoichiometric composition ratio of the silicidelayer 39X to be formed or on the basis of an amount in which a desiredhigh-temperature resistance and a desired work function are obtained.Similarly, the thickness of the alloy film 59 is set by a thicknessrelative to the thickness of the semiconductor layer 33X so that desiredsilicide layer 39X may be formed. The composition ratio and thickness ofthe silicide layer 39 to be formed may be controlled in accordance withthe heating time or temperature of the silicide treatment.

In addition, due to the formation of the silicide layer 39 to which theforeign element 52 is added, a segregation layer (not shown) in whichimpurities (donor/acceptor) contained in the silicon layer 33 aresegregated may be formed at the junction (interface) of the silicidelayer 39 and the silicon layer 33.

After the silicide treatment, the alloy film 59 which has not caused asilicide reaction with the silicon layer is removed by, for example, wetetching.

In addition, the silicide layer 39X may further include elements (e.g.,B, Ge) other than the Si element contained in the silicon layer 33X.

As shown in FIG. 14C, a first electrode layer 25X, a resistance changefilm 21X and a second electrode layer 26X are sequentially deposited onthe silicide layer 39X as constituent parts of the memory element.Electrode layers 25X, 26X are formed by, for example, the CVD method orsputter method. The resistance change film 21X is formed by, forexample, the sputter method, the CVD method, an atomic layer deposition(ALD) method, or a metal-organic CVD (MOCVD) method.

The materials for electrode layers 25X, 26X and the resistance changefilm 21X are selected by the combination of materials whereby theresistance value of the resistance change film 21X reversibly changesand the changed resistance value of the resistance change film 21X isretained in a nonvolatile manner. However, the material for electrodelayers 25X, 26X is not limited as long as the resistance change film 21Xitself reversibly changes its resistance value due to externallyprovided energy (e.g., a voltage or heat) and retains the changedresistance value.

As described above, a metal oxide, a metal compound or organic matter isused for the resistance change film 21X. Thus, a high formationtemperature of about 600° C. to 800° C. may be used, depending on thematerial that forms the resistance change film 21X. In the presentembodiment, the silicide layer 39X formed on the silicon layer 33Xincludes an additional element having an atomic radius greater than theatomic radius of the 3d transition metal element, in addition to the Sielement and the 3d transition metal element. Thus, as shown in FIG. 4 toFIG. 6, crystal grains constituting the silicide layer 39 are renderedmicrocrystal, so that silicide layer 39X has high high-temperatureresistance (heat resistance).

Therefore, in the manufacturing method according to the presentembodiment, agglomeration of metal elements for forming the silicidelayer 39X is not easily caused by the high-temperature thermaltreatment, and the formation of resultant agglomerates in the silicidelayer 39X and silicon layers 32X, 33X thereunder is inhibited. Thediffusion of the metal elements included in the silicide layer 39X intosilicon layers 32X, 33X is also inhibited. Moreover, the silicon layer33X is prevented from being reduced to a thickness smaller than apredetermined thickness due to excessive formation of the silicide layer39X resulting from the high-temperature thermal treatment, and thejunction (interface) of two silicon layers is prevented from beingbroken due to the erosion of two silicon layers 32X, 33X by the silicidelayer 39X.

This reduces the need to increase the thickness of silicon layers 31X,32X, 33X to alleviate the adverse effects of the diffusion of the metalelements and the erosion by the silicide layer.

As shown in FIG. 14D, a mask (not shown) having a predetermined shape isformed on an electrode layer 26Y. For example, each layer under the maskis processed in accordance with the shape of the mask by etching thatuses a reactive ion etching (RIE) method. As a result, electrode layer25Y, 26Y, a resistance change film 21Y, a silicide layer 39Y and siliconlayers 31Y, 32Y, 33Y are sequentially processed, and divided into cellunits in the second direction with a predetermined space. Thus, a stack100 is formed on substrate 11. Formed stack 100 extends in the firstdirection. Simultaneously with the formation of the stack 100,conductive layer is processed, and the interconnect line 60 extending inthe second direction is formed on the substrate 11.

Then, an interlayer insulating film 69 is embedded between adjacentstacks 100 by, for example, the CVD method or a coating method.

In addition, in this step, the stack may be divided in the firstdirection and a interconnect line extending in the second direction maybe formed to form the first memory cell array M1 shown in FIG. 2.However, in a cross-point type memory cell array, the cell unit and thememory cell array are preferably formed in the manufacturing processshown in FIG. 14E and FIG. 14F without dividing stack 100 in the firstdirection immediately after the step shown in FIG. 14D.

As shown in FIG. 14E and FIG. 14F, conductive layer 65X serving as asecond interconnect line is deposited on stack 100 and interlayerinsulating film 69 extending in the first direction. Then, layers toconstitute the cell unit of a second memory cell array are sequentiallydeposited on conductive layer 65X. The stacking order of the layers onconductive layer 65X varies depending on which of the connectionrelations indicated by “a” to “p” of FIG. 10 two cell units shared byone interconnect line (conductive layer 65X) have. For ease ofexplanation, the two cell units have the connection relation indicatedby “a” of FIG. 10 in the case described here.

In the example shown in FIG. 14E, the stacking order of layers 31X′,32X′, 33X′, 25X′, 21X′, 26X′ on a conductive layer 65X is the same asthe stacking order of the layers constituting stack 100. The layersstacked on conductive layer 65X are formed in the same manufacturingprocess as the layers constituting the stack 100, respectively.

When the silicide layer 39X′ is formed above stack 100, the wholesubstrate is subjected to a high-temperature (about 500° C. to 800° C.)thermal treatment. The silicide layer 39Y in the stack 100 is renderedmicrocrystal by the addition of a foreign element, and therefore hashigh-temperature resistance. Thus, in the stack 100 including thesilicide layer 39Y, adverse effects of the high-temperature thermaltreatment, such as the diffusion of the metal elements included in thesilicide layer 39Y and the erosion of the silicon layer 33Y by thesilicide layer 39Y are inhibited.

The stack 100 on the interconnect line 60 and the layers on the stack100 are processed by a photolithographic technique and the RIE method insuch a manner as to ensure the etching selectivity for the interconnectline 60. The stack 100 extending in the first direction is divided intocell units in the first direction with a predetermined space.Simultaneously with the division of the stack in the first direction,The conductive layer 65X on the stack is processed into individualpatterns divided in the first direction, and an interconnect line 65extending in the second direction is formed on the stack disposed on theinterconnect line 60 extending in the first direction.

As shown in FIG. 14G, cell unit CU1 is formed between the interconnectline 60 extending in the first direction and the interconnect line 65extending in the second direction.

In a cell unit CU1, a rectification element (non-ohmic element) 30 has asilicide layer 39 at the top, and the silicide layer 39 is provided onthe top surface of a silicon layer 33. Further, a memory element 20 isprovided on the silicide layer 39.

Moreover, since the layers are etched starting from the upper layer inorder, a stack 100′ is formed on the cell unit CU1 with the interconnectline 65 in between. Similarly to the interconnect line 65, the stack100′ is divided in the first direction with a predetermined space. Inthe step shown in FIG. 14G, the stack 100′ extends in the seconddirection, in the same manner as in FIG. 14E. In the cross-point typememory cell array, the stack 100′ is processed in the second directioninto a cell unit CU2 of a (second-layer) memory cell array to be higherthan the first-layer memory cell array.

Interlayer insulating films are embedded between cell units CU1 adjacentin the first direction and between stacks 100′ adjacent in the firstdirection.

Here, in case memory cell arrays are further provided on stacks 100′,the process similar to the process shown in FIG. 14E to FIG. 14G isrepeated before a predetermined number of memory cell arrays arestacked.

As shown in FIG. 14E to FIG. 14G, the second-layer memory cell array isprocessed simultaneously with the formation of the first-layer memorycell array on the substrate 11.

Thus, the formation of the upper memory cell array and the processing ofthe lower memory cell array are carried out in a common step, so thatthe process of manufacturing the resistance change memory having thecross-point type memory cell array is simpler and its manufacturingcosts are lower than when each memory cell array in each layer(interconnection level) is processed in the first and second directions.

In the case described with FIG. 14A to FIG. 14E, the silicide layer isformed at the top of the rectification element. When silicide layer 39is formed at the bottom of the rectification element as in 12B and FIG.12C, the alloy film formed between the conductive layer 60X and thesilicon layer is subjected to silicidation together with the siliconlayer, so that the silicide layer 39 is formed on the bottom of thesilicon layer. The silicon layer to form the silicide layer 39 may bethe silicon layer 31X, 33X or may be a layer formed separately from thesilicon layer 31X, 33X.

In the case described with FIG. 14B, the alloy film 59 which has notcaused a silicide reaction with the silicon layer is removed by, forexample, wet etching after the silicide treatment. However, the alloyfilm which has not caused a silicide reaction may remain on the silicidelayer 39X for use as the diffusion preventing layer, the adhesive layer,or as part of the electrode of the rectification element or the memoryelement.

For example, as shown in FIG. 14H, the resistance change film 21X andthe second electrode layer 26X may be sequentially deposited asconstituent parts of the memory element on the metal film (alloy film)59 used as the first electrode layer. As a result, the step ofseparately depositing lower electrode (first electrode layer) of thememory element can be eliminated, and the process of manufacturing theresistance change memory can be simpler.

As described above, in the first method of manufacturing the resistancechange memory according to the present embodiment, the silicide layer 39is provided on at least one end (top) or the other end (bottom) ofnon-ohmic element (rectification element) 30. The silicide layer 39includes the Si element 50 and the 3d transition metal element 51, andalso includes the element (additional element) 52 having an atomicradius greater than the atomic radius of the 3d transition metal element51. In this manufacturing method, the silicide layer 39 is formed by thethermal treatment at 500° C. or more for the metal film (alloy film)including the 3d transition metal element 51 and the additional element52 and for the silicon layer.

As shown in FIG. 4 to FIG. 6, the silicide layer 39 included in theresistance change memory according to the present embodiment includesthe additional element 52 and thus has high-temperature resistance.Therefore, even if a high-temperature thermal treatment is included inthe method of manufacturing a semiconductor device such as theresistance change memory, agglomeration of the metal elements (atoms)included in the silicide layer, diffusion of the metal elements intoother constituent elements (e.g., the silicon layer) and the erosion ofother parts by silicide can be inhibited.

As a result, in the resistance change memory according to the presentembodiment, characteristic deterioration of the non-ohmic element causedwhen silicide having low heat resistance, such as the increase of areverse current of the rectification element when a reverse bias isapplied is reduced.

Furthermore, there is no need to increase the thickness of the siliconlayer 33X in order to alleviate effects of the diffusion of the metalelements and the erosion by the silicide layer. Therefore, the thickness(height in the stacking direction) of the non-ohmic element(rectification element) is smaller, and the aspect ratio of the cellunit (stack) is lower.

Thus, the processing (etching) to form the cell unit is relatively easy,and the embedding quality of the interlayer insulating film betweenadjacent cell unit is improved.

As shown in FIG. 14E to FIG. 14G, the aspect ratio increases when twostacked memory cell arrays (cell units) are simultaneously processed, sothat reducing the thickness of the non-ohmic element to hold down theincrease of the aspect ratio is effective.

In addition, since the height of the non-ohmic element is smaller, thereis no need to have a large space between adjacent cell units to ensure amargin for processing. This enables a reduction in the area of thememory cell array of the resistance change memory.

Furthermore, as shown in FIG. 7A and FIG. 7B, the work function ofsilicide can be adjusted by the addition of the additional element 52 toa certain silicide. This enables a reduction in the resistance of theinterface between the silicide layer 39 and the semiconductor layer 33.

As a result, a current loss attributed to the interface resistance isreduced. For example, the upper limit value of the forward current whena forward bias is applied is higher in the rectification element, andthe output of the forward current of the rectification element is higherthan the value of a certain applied voltage. Thus, the current (voltage)that can be supplied to the memory element 20 is higher at a certaindrive voltage applied to a selected cell unit.

As described above, according to the resistance change memorymanufacturing method in the embodiment, a resistance change memory inwhich deterioration of element characteristics is inhibited can beprovided.

(b) Second Manufacturing Method

A second method of manufacturing the resistance change memory accordingto the embodiment is described with FIG. 15A to FIG. 15D. FIG. 15A toFIG. 15D show sectional process views taken along the second directionof a memory cell array in one step of the present manufacturing method.It is to be noted that parts equivalent to the parts described in thefirst manufacturing method are denoted with the same reference numbersand are not described. It is also to be noted that steps equivalent tothe steps in the first manufacturing method described with FIG. 14A toFIG. 14G are not described here.

The second method of manufacturing the resistance change memoryaccording to the present embodiment is different from the firstmanufacturing method in that a metal film including one kind of the 3dtransition metal element 51 is deposited separately from a metal filmincluding at least one kind of the element 52 having an atomic radiusgreater than the atomic radius of the 3d transition metal element 51.

As shown in FIG. 15A, a metal film 57 containing the 3d transition metalelement 51 as the main component is formed on the silicon layer 33X.Further, a metal film 58 containing the additional element 52 as themain component is formed on the metal film 57.

Layers 33X, 57, 58 are thermally treated, so that elements 51, 52 in twometal films 57, 58 cause a silicide reaction with the Si element in thesilicon layer 33X, and the silicide layer 39X is formed on the siliconlayer 33X as in FIG. 14B.

As shown in FIG. 15B, the metal film 58 containing the additionalelement 52 may be deposited on the silicon layer 33X, and the metal film57 containing the 3d transition metal element 51 may be deposited on themetal film 58.

As shown in FIG. 15A and FIG. 15B, in the second method of manufacturingthe resistance change memory according to the present embodiment, asilicide layer which has high-temperature resistance and which canreduce the resistance of the interface with the silicon layer 33X can beformed as in the first manufacturing method described above.

Furthermore, metal films 57, 58 which have not caused a silicidereaction with silicon may remain on the silicide layer 38X for use aspart of the electrode of the memory element.

For example, when the step of removing the metal film which has notcaused a silicide reaction with the silicon layer after the step in FIG.15A is omitted, the metal film 58 can be used for the first electrodelayer (the lower electrode of the memory element).

For example, as shown in FIG. 15C, the resistance change film 21X andthe second electrode layer 26X are sequentially deposited as constituentparts of the memory element on the metal film 58 used as the firstelectrode layer. As a result, the step of separately depositing thefirst electrode layer can be eliminated, and the manufacturing processcan be simplified.

Similarly, if the step of removing the metal film which has not caused asilicide reaction with the silicon layer after the step in FIG. 15B isomitted, the metal film 57 can be used for the first electrode layer(the lower electrode of the memory element).

For example, as shown in FIG. 15D, the resistance change film 21X andthe second electrode layer 26X are sequentially deposited as constituentparts of the memory element on the metal film 57 used as the firstelectrode layer. As a result, the step of separately depositing thefirst electrode layer can be eliminated, and the manufacturing processcan be simplified.

Consequently, according to the second method of manufacturing theresistance change memory in the embodiment, a resistance change memoryin which deterioration of element characteristics is inhibited can beprovided as in the first manufacturing method.

(c) Third Manufacturing Method

A third method of manufacturing the resistance change memory accordingto the embodiment is described with FIG. 16A to FIG. 16D. FIG. 16A toFIG. 16D show sectional process views taken along the second directionof a memory cell array in one step of the present manufacturing method.It is to be noted that parts equivalent to the parts described in thefirst and second manufacturing methods are provided with the samereference numbers and are not described. It is also to be noted thatsteps equivalent to the steps in the first and second manufacturingmethods are not described here.

The third method of manufacturing the resistance change memory accordingto the present embodiment is different from the first and secondmanufacturing methods in that a silicide layer including the Si element50 and the 3d transition metal element 51 is formed and then theadditional element 52 having an atomic radius greater than the atomicradius of the 3d transition metal element 51 is added to the formedsilicide layer.

As shown in FIG. 16A, a silicide layer (hereinafter referred to as abase silicide layer) 37 including the Si element 50 and the 3dtransition metal element 51 is formed on the silicon layer 33X. The basesilicide layer 37 is formed by, for example, a silicide reaction betweenthe silicon layer 33X and the 3d transition metal element. After thebase silicide layer 37 is formed, the metal film 58 is deposited on thesilicide layer 37. The metal film 58 includes the element 52 having anatomic radius greater than the atomic radius of the 3d transition metalelement 51.

The base silicide layer 37 and the metal film 58 are thermally treated,and the element 52 included in the metal film 58 diffuses into the basesilicide layer 37. Diffused element 52 chemically reacts (is bonded)with the Si element 50 and the metal element 51 in the silicide layer37. Thus, the element 52 is added into the base silicide layer 37including the Si element 50 and the 3d transition metal element 51.

Thus, in the same manner as shown in FIG. 14B, the silicide layer 39including the Si element 50, the 3d transition metal element 51, and theelement 52 having an atomic radius greater than the atomic radius of theelement 51 is formed on the silicon layer 33X.

As shown in FIG. 16B, the metal film 57 containing the 3d transitionmetal element 51 as the main component may be deposited on a compoundlayer 38 including the Si element 50 and the additional element 52. Inthis case, the Si element 50 in the compound layer 38 and the 3dtransition metal element 51 in the metal film 57 cause a silicidereaction due to a thermal treatment, and the silicide layer 39 shown inFIG. 14B is formed. In addition, the compound layer 38 may be a silicidelayer composed of the Si element 50 and the additional element 52,depending on the kind of selected additional element 52.

As shown in FIG. 16A and FIG. 16B, in the third method of manufacturingthe resistance change memory according to the present embodiment, asilicide layer which has high-temperature resistance and which canreduce the resistance of the interface with the silicon layer 33X can beformed as in the first and second manufacturing methods.

Furthermore, metal films 57, 58, which have not diffused into thesilicide layer, may remain on the silicide layer 38X for use as part ofthe electrode of the memory element.

For example, when the step of removing the metal film which has notcaused a silicide reaction with the silicon layer after the step in FIG.16A is omitted, the metal film 58 can be used for the first electrodelayer (the lower electrode of the memory element).

For example, as indicated by FIG. 16C, the resistance change film 21Xand the second electrode layer 26X are sequentially deposited asconstituent parts of the memory element on the metal film 58 used as thefirst electrode layer. As a result, the step of separately depositingthe first electrode layer can be eliminated, and the manufacturingprocess can be simplified.

Similarly, when the step of removing the metal film which has not causeda silicide reaction with the silicon layer after the step in FIG. 16B isomitted, the metal film 57 can be used for the first electrode layer(the lower electrode of the memory element).

For example, as shown in FIG. 16D, the resistance change film 21X andthe second electrode layer 26X are sequentially deposited as constituentparts of the memory element on the metal film 58 used as the firstelectrode layer. As a result, the step of separately depositing thefirst electrode layer can be eliminated, and the manufacturing processcan be simplified.

Consequently, according to the third method of manufacturing theresistance change memory in the embodiment, a resistance change memoryin which deterioration of element characteristics is inhibited can beprovided as in the first and second manufacturing methods.

(d) Fourth manufacturing method

A fourth method of manufacturing the resistance change memory accordingto the embodiment is described with FIG. 17A and FIG. 17B. FIG. 17A andFIG. 17B show sectional process views taken along the second directionof a memory cell array in one step of the present manufacturing method.It is to be noted that parts equivalent to the parts described in thefirst to third manufacturing methods are provided with the samereference numbers and are not described. It is also to be noted thatsteps equivalent to the steps in the first to third manufacturingmethods are not described here.

The fourth method of manufacturing the resistance change memoryaccording to the present embodiment is different from the first to thirdmanufacturing methods in that an element having an atomic radius greaterthan the atomic radius of a 3d transition metal element is added into asilicide layer by ion implantation.

As shown in FIG. 17A, a predetermined dose amount of ionized element 52is implanted the into the base silicide layer 37 including the Sielement 50 and the 3d transition metal element 51 by an ion implantationmethod. The silicide layer 37 into which the element 52 has beenimplanted is thermally treated. As a result of this thermal treatment,the element 52 implanted into the silicide layer 37 is activated in thesilicide layer 37, and added element 52 chemically reacts (is bonded)with the Si element 50 and/or the 3d transition metal element 51 in thesilicide layer 37.

Thus, as shown in FIG. 14B, the silicide layer 39 including the Sielement 50, the 3d transition metal element 51, and the element 52having an atomic radius greater than the atomic radius of the element 51is formed on the silicon layer 33X.

As shown in FIG. 17B, ionized 3d transition metal element 51 may beimplanted into the compound layer 38 including the Si element 50 and theadditional element 52. Then, a thermal treatment is carried out as shownin FIG. 17A, so that implanted 3d transition metal element 51 causes asilicide reaction with the Si element 52 in compound layer 38, and thesilicide layer 39 is formed on the silicon layer 33X.

Moreover, both the 3d transition metal element 51 and the additionalelement 52 may be implanted into the silicon layer 33X by the ionimplantation method. In this case as well, the silicide layer 39 isformed by carrying out a thermal treatment.

As shown in FIG. 17A and FIG. 17B, in the fourth method of manufacturingthe resistance change memory according to the present embodiment, asilicide layer which has high-temperature resistance and which canreduce the resistance of the interface with the silicon layer 33X can beformed as in the first to third manufacturing methods.

Furthermore, if a silicide layer including the additional element 52 isformed by the ion implantation method as in the fourth manufacturingmethod described above, the silicide layer 39 including the additionalelement can be formed at a lower heating temperature than when theadditional element 52 is formed in the silicide layer only by thethermal treatment. That is, in the fourth manufacturing method, thetemperature of the thermal treatment for forming the silicide layer 39can be lower.

Thus, when a plurality of memory cell arrays are stacked as in the caseof the cross-point type memory cell arrays, heat for forming silicidelayer 39 can be inhibited from being repeatedly provided to the lowerlayer memory cell arrays. This makes it possible to reduce thedeterioration of element characteristics resulting from the history of aplurality of thermal treatments and reduce the difference of elementcharacteristics between the upper layer element and the lower layerelement.

Furthermore, the thermal treatment for forming the silicide layer 39 caninhibit impurities (e.g., carbon) in the interlayer insulating film andmetal elements included in interconnect lines and the electrodes fromdiffusing into semiconductor layers 31X, 32X, 33X or the resistancechange film 21X. This makes it possible to inhibit the deterioration ofelement characteristics resulting from the diffusion of impurities.

Consequently, according to the fourth method of manufacturing theresistance change memory in the embodiment, a resistance change memoryin which deterioration of element characteristics is inhibited can beprovided as in the first to third manufacturing methods.

(e) Fifth Manufacturing Method

A fifth method of manufacturing the resistance change memory accordingto the embodiment is described with FIG. 18A and FIG. 18B. FIG. 18A andFIG. 18B show sectional process views taken along the second directionof a memory cell array in one step of the present manufacturing method.It is to be noted that parts equivalent to the parts described in thefirst to fourth manufacturing methods are provided with the samereference numbers and are not described. It is also to be noted thatsteps equivalent to the steps in the first to fourth manufacturingmethods are not described here.

In the cases described in the first to fourth manufacturing methods, thesilicide layer including the Si element, the 3d transition metal elementand the additional element is formed before a plurality of layers toconstitute the cell unit are processed into a stack of a predeterminedshape (size). However, the silicide layer may be formed after the stackis formed.

In the case described with FIG. 18A, a non-ohmic element (rectificationelement) forming a cell unit is stacked on a memory element.

For example, as shown in FIG. 18A, the electrode layer 25Y, theresistance change film 21Y and the electrode layer 26Y are sequentiallydeposited on the conductive layer 60. Further, three silicon layers 31Y,32Y, 33Y are sequentially deposited on the electrode layer 26Y.

As shown in the step shown in FIG. 14D, the stack 100 is formed by thephotolithographic technique and the RIE method. Then, the interlayerinsulating film 69 is embedded between adjacent stacks 100.

After the stack 100 is formed, the metal film 59, for example, isdeposited on semiconductor layer 33Y and on the interlayer insulatingfilm 69. The metal film 59 includes the 3d transition metal element 51,and the element 52 having an atomic radius greater than the atomicradius of the 3d transition metal element.

Furthermore, the 3d transition metal element included in the metal film59 causes a silicide reaction with the Si element included in thesilicon layer 33Y due to the thermal treatment for the metal film 59 andthe silicon layer 33Y, and a silicide layer is formed. The additionalelement in the metal film 59 is added into the silicide layer.

Thus, the silicide layer 39 including an Si element, a 3d transitionmetal element, and an element having an atomic radius greater than theatomic radius of the 3d transition metal element is formed on the end(top) of the silicon layer 33Y after stack 100 is formed.

The step in which the silicide layer used in the present embodiment isformed after being processed into a stack as in the fifth method ofmanufacturing the resistance change memory according to the presentembodiment is effective in the structure in which the rectificationelement 30 is stacked on the memory element 20 as in cell unit CU shownin FIG. 12D or FIG. 12F.

However, even when a memory element is stacked on a rectificationelement, silicon layers 31Y, 32Y, 33Y constituting the rectificationelement may be once processed, and a silicide layer may be formed by amethod similar to that in FIG. 18A, as shown in FIG. 18B.

In the case described here, the above-described first manufacturingmethod is used to form the silicide layer including the 3d transitionmetal element 51 and the additional element 52 after the processing ofthe stack. However, it goes without saying that the above-describedsecond to fourth manufacturing methods can also be used to form thesilicide layer after the processing of the stack as in FIG. 18A to FIG.18C.

Consequently, according to the fifth method of manufacturing theresistance change memory in the embodiment, a resistance change memoryin which deterioration of element characteristics is inhibited can beprovided as in the first and second manufacturing methods.

(4) Operation

The operation of the resistance change memory is described next.

FIG. 19 shows two memory cell arrays.

Memory cell array M1 corresponds to memory cell array M1 shown in FIG.2, and memory cell array M2 corresponds to memory cell array M2 shown inFIG. 2. The connection between the memory element and the non-ohmicelement (e.g., a rectification element) in cell unit CU1, CU2corresponds to “a” of FIG. 10.

A. Set Operation

First described is the case where a writing (set) operation is performedon selected cell unit CU1-sel in memory cell array M1.

The initial state of selected cell unit CU1-sel is an erased (reset)state.

For example, the reset state is a high-resistance state (100 kΩ to 1MΩ), and the set state is a low-resistance state (1 kΩ to 10 kΩ).

Selected interconnect line L2 (i) is connected to high-potential-sidepower supply potential Vdd, and selected interconnect line L1 (j) isconnected to low-potential-side power supply potential Vss.

Among first interconnect lines from the substrate side, unselectedinterconnect lines L1 (j−1), L1 (j+1) other than selected interconnectline L1 (j) are connected to power supply potential Vdd. Among secondinterconnect lines from the substrate side, unselected interconnectlines L2 (i+1) other than selected interconnect line L2 (i) areconnected to power supply potential Vss.

Furthermore, third unselected interconnect lines L3 (j−1), L3 (j), L3(j+1) from the substrate side are connected to power supply potentialVss.

In this case, a forward bias is applied to the rectification element(e.g., a diode) in selected cell unit CU1-sel. Thus, set current I-setfrom a constant current source 12 runs through selected cell unitCU1-sel, and the resistance value of the memory element in selected cellunit CU1-sel changes from the high-resistance state to thelow-resistance state.

Here, in the set operation, a voltage of, for example, about 1 V to 2 Vis applied to the memory element in selected cell unit CU1-sel, and thedensity of set current I-set running through the memory element(high-resistance state) is set at a value ranging, for example, from1×10⁵ to 1×10⁷ A/cm². In addition, when the change of the resistancevalue of the memory element in the set operation depends on the pulsewidth of the current, the pulse width of a set current is appropriatelyset at a predetermined pulse width.

On the other hand, a reverse bias is applied to the rectificationelement (diode) in the cell unit which is connected between unselectedinterconnect lines L1 (j−1), L1 (j+1) and unselected interconnect lineL2 (i+1), among unselected cell units CU1-unsel in memory cell array M1.

Similarly, a reverse bias is applied to the rectification element(diode) in the cell unit which is connected between selectedinterconnect line L2 (i) and unselected interconnect lines L3 (j−1), L3(j), L3 (j+1), among unselected cell units CU2-unsel in memory cellarray M2.

Therefore, the following characteristics are required for therectification element in the cell unit: a sufficiently low current whena reverse bias is applied, and a sufficiently high breakdown voltage.

B. Reset Operation

Next described is the case where an erasing (reset) operation isperformed on selected cell unit CU1-sel in memory cell array M1.

Selected interconnect line L2 (i) is connected to high-potential-sidepower supply potential Vdd, and selected interconnect line L1 (j) isconnected to low-potential-side power supply potential Vss.

Among first interconnect lines from the substrate side, unselectedinterconnect lines L1 (j−1), L1 (j+1) other than selected interconnectline L1 (j) are connected to power supply potential Vdd. Among secondinterconnect lines from the substrate side, unselected interconnectlines L2 (i+1) other than selected interconnect line L2 (i) areconnected to power supply potential Vss.

Furthermore, third unselected interconnect lines L3 (j−1), L3 (j), L3(j+1) from the substrate side are connected to power supply potentialVss.

In this case, a forward bias is applied to the rectification element(e.g., a diode) in selected cell unit CU1-sel. Thus, reset currentI-reset from a constant current source 12 runs through selected cellunit CU1-sel, and the resistance value of the memory element in selectedcell unit CU1-sel changes from the low-resistance state to thehigh-resistance state.

Here, in the reset operation, a voltage of, for example, about 1 V to 3V is applied to the memory element in selected cell unit CU1-sel, andthe density of reset current I-reset running through the memory element(low-resistance state) is set at a value ranging, for example, from1×10³ to 1×10⁶ A/cm². In addition, when the change of the resistancevalue of the memory element in the reset operation depends on the pulsewidth of the current, the pulse width of a reset current isappropriately set at a predetermined pulse width.

On the other hand, a reverse bias is applied to the rectificationelement (diode) in the cell unit which is connected between unselectedinterconnect lines L1 (j−1), L1 (j+1) and unselected interconnect lineL2 (i+1), among unselected cell units CU1-unsel in memory cell array M1.

Similarly, a reverse bias is applied to the rectification element(diode) in the cell unit which is connected between selectedinterconnect line L2 (i) and unselected interconnect lines L3 (j−1), L3(j), L3 (j+1), among unselected cell units CU2-unsel in memory cellarray M2.

Therefore, the following characteristics are required for therectification element in the cell unit: a sufficiently low current whena reverse bias is applied, and a sufficiently high breakdown voltage.

In addition, the value of set current I-set and the value of resetcurrent I-reset are different from each other. Moreover, when theset/reset operation of the memory element depends on the pulse width ofthe current/voltage, the pulse width of the set current and the pulsewidth of the reset current are different from each other. Further, thevalue/time of the voltage applied to the memory element in selected cellunit CU1-sel for generating these currents depends on the materialsconstituting the memory element.

C. Read Operation

Next described is the case where a read operation is performed onselected cell unit CU1-sel in memory cell array M1.

Selected interconnect line L2 (i) is connected to high-potential-sidepower supply potential Vdd, and selected interconnect line L1 (j) isconnected to low-potential-side power supply potential Vss.

Among first interconnect lines from the substrate side, unselectedinterconnect lines L1 (j−1), L1 (j+1) other than selected interconnectline L1 (j) are connected to power supply potential Vdd. Among secondinterconnect lines from the substrate side, unselected interconnectlines L2 (i+1) other than selected interconnect line L2 (i) areconnected to power supply potential Vss.

Furthermore, third unselected interconnect lines L3 (j−1), L3 (j), L3(j+1) from the substrate side are connected to power supply potentialVss.

In this case, a forward bias is applied to the rectification element(e.g., diode) in selected cell unit CU1-sel. Thus, read current I-readfrom a constant current source 12 runs through the memory element inselected cell unit CU1-sel (the high-resistance state or thelow-resistance state).

Therefore, for example, by detecting a potential change in a sense nodewhen read current I-read is running through the memory element, data(resistance value) in the memory element can be read.

Here, the value of read current I-read is much lower than the value ofset current I-set and the value of reset current I-reset so that theresistance value of the memory element may not change in reading. Whenthe change of the resistance value of the memory element depends on thepulse width of the current, the pulse width of the read current is setat a pulse width that does not change the resistance value of the memoryelement.

In reading, as in setting/resetting, a reverse bias is applied to therectification element (diode) in the cell unit which is connectedbetween unselected interconnect lines L1 (j−1), L1 (j+1) and unselectedinterconnect line L2 (i+1), among unselected cell units CU1-unsel inmemory cell array M1.

A reverse bias is also applied to the rectification element (diode) inthe cell unit which is connected between selected interconnect line L2(i) and unselected interconnect lines L3 (j−1), L3 (j), L3 (j+1), amongunselected cell units CU2-unsel in memory cell array M2.

Thus, the following characteristics are required for the rectificationelement in the cell unit: a sufficiently low current when a reverse biasis applied, and a sufficiently high breakdown voltage.

The set/reset operation and read operation of the resistance changememory are performed as described above.

As described above, the resistance change memory according to thepresent embodiment has silicide layer 39 on at least one of both ends ofthe non-ohmic element (e.g., a rectification element) forming the cellunit as shown in FIG. 3. The silicide layer 39 includes the Si element50, the 3d transition metal element 51 that combines with the Si element50 to form silicide, and the additional element (foreign element) 52having an atomic radius greater than the atomic radius of the 3dtransition metal element 51.

Since silicide layer 39 included in the resistance change memoryaccording to the present embodiment has high high-temperature resistance(high heat resistance) owing to the addition of the foreign element, theagglomeration and diffusion of the metal elements (atoms) included inthe silicide layer and the erosion of silicon layer by the silicidelayer are not easily caused.

In the resistance change memory according to the present embodiment,adverse effects of such a high-temperature thermal treatment on thesilicide layer can be inhibited, so that, for example, a reverse currentat the time of reverse bias application can be reduced, and a highbreakdown voltage can be ensured.

Thus, in the resistance change memory according to the presentembodiment, even if a high-temperature thermal treatment is carried outin its manufacturing process, deterioration in the reverse biascharacteristics of the rectification element can be inhibited. Since thedeterioration in the reverse bias characteristics of the unselected cellunit can be inhibited, wrong operation (e.g., wrong writing) of theunselected cell unit, such as the supply of an excessive current to theunselected cell unit, can be decreased.

In addition, in any of the set/reset operation and read operation, thenumber of unselected cell units is greater than the number of selectedcell units.

Therefore, if the reverse bias characteristics of the unselected cellunit are deteriorated, the total amount of the reverse current generatedin the whole memory cell array is significantly great. As a result, thepower consumption of cross-point type memory cell array 2 in FIG. 2 isincreased.

On the contrary, since the deterioration in the reverse biascharacteristics of the rectification element can be inhibited in theresistance change memory according to the present embodiment, theincrease of the power consumption of the resistance change memory can beinhibited.

The work function of the silicide layer included in the resistancechange memory according to the present embodiment can be modulated bythe addition of the foreign element to silicide. That is, by properlyselecting the kind and addition amount of the foreign element added to acertain silicide, the interface resistance of the silicon-silicidejunction can be reduced, and a current loss resulting from the interfaceresistance can be reduced.

Thus, in the resistance change memory according to the presentembodiment, the upper limit of the forward current when a forward biasis applied can be improved, and the forward current of the rectificationelement at a certain forward bias voltage can be higher.

Therefore, in the resistance change memory according to the presentembodiment, a current of an intensity sufficient to accurately performthe set/reset operation can be supplied to the memory element of theselected cell unit. The improvement of the characteristics of therectification element when a forward bias is applied can also contributeto the reduction of the power consumption of the resistance changememory.

Consequently, characteristic deterioration of constituent elements(e.g., a rectification element) including silicide can be inhibited.

As described above, the silicide layer 39 including the Si element 50,the 3d transition metal element 51 that combines with the Si element 50to form silicide, and the additional element 52 having an atomic radiusgreater than the atomic radius of element 51 is used to form thenon-ohmic element (e.g., a rectification element). This inhibits thechange of the quality of the silicide layer attributed to thehigh-temperature thermal treatment and resultant adverse effects on theelements, reduces the interface resistance of the silicide layer, andimproves the electric characteristics of the elements.

Thus, according to the resistance change memory in the embodiment of thepresent invention, deterioration of the element characteristics of theresistance change memory can be inhibited.

<Modification>

A modification of the resistance change memory according to theembodiment is described with FIG. 20A to FIG. 21.

(1) Modification 1

Modification 1 of the resistance change memory according to theembodiment is described with FIG. 20A and FIG. 20B.

FIG. 20A schematically shows a modification of the silicide layer usedin the cell unit.

In the modification shown in FIG. 20A, a silicide layer 39D includes twoor more kinds of additional elements 52, 53 selected from theabove-mentioned additional element group.

Atomic radius r3 of the second additional element 53 may be greater thanatomic radius r2 of the first additional element 52, or may be equal toor less than atomic radius r2.

Here, this modification is described taking as an example the case wherePd and Pt are added to NiSi_(y).

In case a cross-point type memory cell array of the resistance changememory is provided above a substrate in which peripheral circuits areformed so that an interlayer insulating film intervenes therebetween, athermal treatment for forming silicide may cause deterioration of theelement formed by a front-end process as in the case of, for example,the effect of slipping into the edge of an element isolation insulatingfilm. Moreover, in, for example, a back-end process for forming a memorycell array, the temperature used for the thermal treatment is preferablylowered to the extent possible.

As has been described with FIG. 4, the temperature of Pd-added NiSi_(y)(Ni_(1-x)Pd_(x)Si_(y)) at which a silicide reaction is caused is higherthan that of Pt-added NiSi_(y) (Ni_(1-x)Pt_(x)Si_(y)). In other words,Ni_(1-x)Pt_(x)Si_(y) can be formed at a relatively low heatingtemperature.

Furthermore, Ni_(1-x)Pd_(x)Si_(y) has lower electric resistance andhigher high-temperature resistance than Ni_(1-x)Pt_(x)Si_(y). WhenNi_(1-x)Pd_(x)Si_(y) and Ni_(1-x)Pt_(x)Si_(y) are combined togetherusing such a characteristic difference, silicide which maintains highhigh-temperature resistance and low electric resistance and which can beformed at a low temperature can be provided.

In NiSi_(y) including both Pt and Pd, the addition amount of Pt has onlyto be greater than the addition amount of Pd to decrease the reactiontemperature (heating temperature) of silicide layer 39D.

Moreover, in NiSi_(y) including both Pt and Pd, the addition amount ofPd has only to be greater than the addition amount of Pt to decreaseelectric resistance and improve high-temperature resistance.

Thus, by adding two or more kinds of additional elements to a certainsilicide, the characteristics of the silicide layer 39D can be adjustedto better suit the operation characteristics and manufacturing processof the resistance change memory.

As a result, the element of the resistance change memory formed in boththe front-end process and back-end process can be inhibited fromcharacteristic deterioration due to a high-temperature thermaltreatment.

FIG. 20B schematically shows a modification different from themodification in FIG. 20A.

Silicide layer 39E to which a foreign element is added is formed by, forexample, the heating treatment of a metal film and a Si element or byion implantation of an element into a layer including Si, in accordancewith the manufacturing method described above.

Thus, SiC, SiGe or SiSn, for example, is used for the layer as a baselayer including Si. These substances are subjected to silicidation, or aforeign element is added to these substances.

Furthermore, part of the N-type silicon layer or P-type silicon layermay be silicidated depending on the structure and characteristics of thenon-ohmic element, and a silicide layer 39E may be thereby formed.Therefore, an element (e.g., P or As) serving as a donor for Si or anelement (e.g., B) serving as an acceptor for Si may be included in thesilicide layer 39E.

Moreover, an oxide film or nitride film may be formed on the surface ofthe silicon layer in the process of manufacturing the memory.

Thus, as shown in FIG. 20B, silicide layer 39E may include one or morekinds of elements 54 derived from a layer (base layer) including a Sielement for forming the silicide layer 39E, such as C, Ge, Sn, P, As, B,O and N, in addition to the Si element 50, the 3d transition metalelement 51 and the additional element 52.

These elements 54 are mainly lattice-substituted for the Si element 50.

It goes without saying that effects substantially similar to the effectsobtained by the resistance change memories described in Basic exampleand Example can be obtained by the resistance change memory inModification 1 shown in FIG. 20A and FIG. 20B.

(2) Modification 2

Modification 2 of the resistance change memory according to theembodiment is described with FIG. 21A to FIG. 21C.

For a interconnect line used as a word line/bit line, silicide may beused instead of a metal such as Cu or Al or a metal compound.

Therefore, a silicide layer including a Si element, a 3d transitionmetal element and an additional element may be used for interconnectlines 60, 65.

In FIG. 21A, a lower interconnect line is formed of the silicide layer39. In FIG. 21B, an upper interconnect line is formed of the silicidelayer 39. In FIG. 21C, both of two interconnect lines are formed of thesilicide layers 39.

In addition, interconnect line 60, 65 may have a stack structureincluding a metal layer and silicide layer 39.

It goes without saying that effects substantially similar to the effectsobtained by the resistance change memories described in Basic exampleand Example can be obtained by the resistance change memory inModification 2 shown in FIG. 21A to FIG. 21C.

<Application>

An application of the embodiment is described with FIG. 22 to FIG. 26.

(1) Transistor

In the resistance change memory, memory cell array 2 shown in FIG. 2 isformed by, for example, a back-end process. On the other hand, fieldeffect transistors (FET) that configure peripheral circuits such as thecontrol circuits 3, 4 are formed by a front-end process. As shown inFIG. 22, field effect transistor Tr of the peripheral circuit is formedon a semiconductor substrate (silicon substrate) under the memory cellarray 2.

FIG. 22 shows one example of the sectional structure of field effecttransistor Tr used in the peripheral circuit. A section of the fieldeffect transistor in a channel length direction is shown in FIG. 22.

As shown in FIG. 22, the same material as that of the silicide layerincluded in the cell unit according to the embodiment may be used forgate electrodes 73, 39 ₁ of field effect transistor Tr and forsource/drain electrodes 39 ₂, 39 ₃ of field effect transistor Tr.

A P-well 71A and an N-well 71B are provided in a semiconductor substrate70. The P-well 71A and N-well 71B are electrically isolated from eachother by an element isolation insulating film 79 in the semiconductorsubstrate 70.

An N-channel field effect transistor Tr is provided in the P-well 71A. AP-channel field effect transistor is provided in the N-well 71B.P-channel and N-channel field effect transistors are substantially thesame in configuration. Therefore, the structure of transistor Tr in theP-well 71A is described here.

Two diffusion layers 74, 75 are provided in P-well 71A. Diffusion layers74, 75 are used as the source/drain of transistor Tr. Source/drainelectrodes 39 ₂, 39 ₃ are provided on the surfaces of diffusion layers74, 75.

A gate insulating film 72 is provided on the surface of the well 71between two diffusion layers 74, 75. A gate electrode 73, 39 ₁ areprovided on the gate insulating film 72. The top of the gate electrodeis formed of the silicide layer 39 ₁, and the bottom of the gateelectrode is formed of the silicon layer 73.

A sidewall insulating film 76 is provided on the side portions of gateelectrode 73, 39 ₁.

Contacts CP1, CP2, CP3 are provided on gate electrodes 73, 39 ₁ andsource/drain electrodes 39 ₂, 39 ₃, respectively.

Electrodes 73, 39 ₁, 39 ₂, 39 ₃ are connected to interconnect lines M1,M2, M3 via contacts CP1, CP2, CP3.

Contacts CP1, CP2, CP3 and interconnect lines M1, M2, M3 are provided ininterlayer insulating films 77A, 77B. A metal such as W is used forcontacts CP1, CP2, CP3.

An upper electrode 39 ₁ of the gate electrode and source/drainelectrodes 39 ₂, 39 ₃ are formed of silicide layers 39 ₁, 39 ₂, 39 ₃ inwhich a foreign element (additional element) is added to silicideincluding an Si element and a 3d transition metal element.

In silicide layers 39 ₁, 39 ₂, 39 ₃ used for the field effecttransistor, the atomic radius of the added foreign element is greaterthan the atomic radius of the 3d transition metal element, similarly tothe silicide layer used for the cell unit described with FIG. 3. Inaddition, one or more kinds of elements may be added to silicide layers39 ₁, 39 ₂, 39 ₃.

The field effect transistor shown in FIG. 22 is formed by the followingmanufacturing method.

FIG. 23 shows one example of the field effect transistor manufacturingmethod.

As shown in FIG. 23, wells 71A, 71B and the element isolation insulatingfilm 79 are formed in the semiconductor substrate (silicon substrate)70.

The gate insulating film 72 is formed on the surfaces of wells 71A, 71Bby, for example, a thermal oxidation method or the CVD method. A siliconlayer is deposited on the gate insulating film 72 by, for example, theCVD method. The silicon layer is processed into a gate electrode 73A ofa predetermined shape by the photolithographic technique and the RIEmethod.

Furthermore, the gate electrode 73A is used as a mask, so that diffusionlayers 74, 75 are formed in wells 71A, 71B by the ion implantationmethod. When an N-type diffusion layer is formed in the P-well 71A, thesurface of the well 71B is covered with a mask (resist). In contrast,when a P-type diffusion layer is formed in the N-well 71B, the surfaceof the P-well 71A is covered with a mask (resist).

After diffusion layers (source/drain) 74, 75 are formed in the P-well71A, the sidewall insulating film 76 is formed on the side surface ofthe gate electrode 73A by the CVD method and the RIE (etch back) method.Then, the gate electrode 73A having a silicon single-layer structure andthe surfaces of diffusion layers 74, 75 in the silicon substrate aresubjected to silicidation. When the transistor formed in the P-well isonly subjected to silicidation, the surface of the N-well 71B is coveredwith the mask (insulating film) 78, as shown in FIG. 23.

As shown in FIG. 23, the metal film 59 including a 3d transition metalelement and other elements (additional elements) is formed on the gateelectrode 73A and diffusion layers 74, 75 by the sputter method or theCVD method, in the same manner as in the manufacturing method shown inFIG. 14A and FIG. 14B. Then, the substrate 70 is thermally treated, andthe metal film 59 and silicon cause a silicide reaction.

However, any one of the second to fourth manufacturing methods describedin Example may be used as the method of forming a silicide layer in thegate electrode of the transistor.

Thus, as shown in FIG. 22, the silicide layer 39 ₁ is formed on the gateelectrode 73 of the transistor. Moreover, silicide layers 39 ₂, 39 ₃ areformed as source/drain electrodes on the surfaces of diffusion layers74, 75 of the transistor.

Silicide layer 39 ₁, 39 ₂, 39 ₃ includes a Si element, a 3d transitionmetal element, and an additional element having an atomic radius greaterthan the atomic radius of the 3d transition metal element. Similarly tothe treatment for the transistor in the P-well 71A, the transistorformed in the N-well 71B is subjected to silicidation.

In the P-well 71A, diffusion layers 74, 75 as the source/drain ofN-channel transistor are made of N-conductivity-type silicon. In theN-well 71B, the diffusion layers as the source/drain of P-channeltransistor are made of P-conductivity-type silicon. Thus, in theP-channel transistor and the N-channel transistor, the 3d transitionmetal element and the additional element for forming silicide layers 39₁, 39 ₂, 39 ₃ may vary in consideration of the work function ofsilicide, depending on the P-type or N-type diffusion layers as thesource/drain. Moreover, the silicide layers in the P-channel transistorand the N-channel transistor may include the same additional element. Inthis case, the P-well and the N-well may be subjected to silicidation atthe same time.

Then, after the alloy film which has not caused a silicide reaction withSi is removed, an interlayer insulating film and a interconnect line,for example, are formed over transistor Tr by a known technique. Thus,the field effect transistor according to the application is completed.

As described above, in the Application shown in FIG. 22 and FIG. 23, thesilicide layer 39 ₁, 39 ₂, 39 ₃ including the Si element, the 3dtransition metal element and the additional element is used for the gateelectrode or the source/drain electrodes of the transistor. The atomicradius of the additional element is greater than the atomic radius ofthe 3d transition metal element.

In the application, a silicide layer having high high-temperatureresistance is used for each of electrodes 39 ₁, 39 ₂, 39 ₃. Thus, asdescribed above, even if a high-temperature thermal treatment is carriedout in the back-end process for forming a memory cell array, the element(e.g., the FET on the substrate) which is formed in the front-endprocess and which includes the silicide layer is inhibited fromdeteriorating in characteristic due to the high-temperature thermaltreatment.

Diffusion layers 74, 75 and the lower part 73A of the gate electrode aremade of silicon. The silicide layer 39 ₁, 39 ₂, 39 ₃ to which a foreignelement is added can reduce the interface resistance of thesilicon-silicide junction, for example, the junction of the diffusionlayer and the source/drain electrode.

In the gate electrode, the resistance of the interface between the upperpart of the gate electrode for which the silicide layer 39 ₁ is used andthe lower part of the gate electrode for which silicon layer 73 is usedis reduced. The decrease of a voltage due to the interface resistance isreduced, so that a gate voltage applied to the gate electrode 73 can bedecreased, and a channel can be formed under the gate electrode 39 ₁, 73at a low gate voltage without any adverse effects of the interfaceresistance.

Similarly, the resistance of the interface between the diffusion layers74, 75 formed in the silicon substrate 70 and the source/drainelectrodes 39 ₁, 39 ₂ is reduced. As a result, the drain current of thefield effect transistor at a certain supply potential increases.

In the example described here, the silicide layer 39 ₁, 39 ₂, 39 ₃ towhich a foreign element is added is used for the field effect transistorof the peripheral circuit of the resistance change memory. However, thesilicide layer may be applied to the constituent element on thesubstrate formed by the front-end process other than the field effecttransistor.

Furthermore, silicide layer 39 ₁, 39 ₂, 39 ₃ described in the presentembodiment may be used for a peripheral circuit of other semiconductormemories or a field effect transistor as a constituent element of asemiconductor integrated circuit (e.g., a logic circuit).

As described above, in the resistance change memory according to theembodiment, at least one kind of element having an atomic radius greaterthan the atomic radius of a 3d transition metal element is added to asilicide layer composed of Si and the 3d transition metal element. Inthe application, silicide layers 39 ₁, 39 ₂, 39 ₃ are not only used forthe memory cell arrays but also used for peripheral circuits formed onthe silicon substrate such as the gate electrodes and the source/drainelectrodes of the field effect transistor.

Consequently, as shown in FIG. 22 and FIG. 23, characteristicdeterioration of the element used in the resistance change memory canalso be inhibited in the application of the embodiment.

(2) Select Transistor

In Basic example and Example, the resistance change memory having thecross-point type memory cell array has been mainly described, and thecell unit of this memory is composed of the memory element and thenon-ohmic element. However, depending on the kind of resistance changememory, a cell unit may be composed of one memory element and at leastone transistor.

In the example shown in FIG. 24, one cell unit has a so-called a 1T+1Rstructure composed of one memory element 20 and one transistor STr. Thetransistor (hereinafter referred to as a select transistor) is used as aselective element for the memory element. The cell unit including suchthe select transistor STr is used in, for example, an MRAM or PCRAM. Inaddition, two or more select transistors may be provided for one memoryelement.

In the cell unit shown in FIG. 24, silicide layers 39 ₁, 39 ₂, 39 ₃described in the present embodiment are used for the gate electrode andthe source/drain electrodes of the select transistor STr. The structureof the select transistor STr is substantially the same as the structureof transistor Tr in the peripheral circuit shown in FIG. 22, and thedifference therebetween is therefore only described here.

The select transistor STr is a field effect transistor formed on asemiconductor substrate (e.g., a silicon substrate).

The memory element 20 is provided on an upper layer of select transistorSTr via interlayer insulating films 77A, 77B.

One end of the memory element 20 is electrically connected to first bitline BL via contact V1. The other end of the memory element 20 iselectrically connected to one end (source/drain) 39 ₂, 75 of a currentpath of select transistor STr via an intermediate interconnect line MOand a contact CP1.

The other end (source/drain) 39 ₃, 74 of the current path of the selecttransistor STr is electrically connected to second bit line bBL via acontact CP2.

The gate electrode 39 ₁, 73 of the select transistor STr is connected tothe word line. In the example shown in FIG. 24, the gate electrode 39 ₁,73 is used as word line WL, and extends in the channel width direction.

The method of forming silicide layers 39 ₁, 39 ₂, 39 ₃ in the gateelectrode and the source/drain electrodes of select transistor STr issimilar to the manufacturing method described with FIG. 23, and istherefore not described here.

In an MRAM or PCRAM, in writing or reading data, a potential is appliedto the gate electrode (word line) of the select transistor in theselected cell unit, and the select transistor STr is turned on. A writecurrent or read current is supplied to the memory element 20 via thecurrent path (channel) of select transistor STr in an on-state.

For example, when a spin-injection magnetization inversion method isused for the operation of writing into the MRAM, the running directionof current I to be supplied to the memory element (MTJ element) ischanged depending on the data to be written. Moreover, in the PCRAM, thewrite current I is supplied to the memory element 20 to provide a heatquantity for changing the crystal phase of resistance change film of thememory element 20.

Thus, when the memory is in operation, the write current or read currentruns through the silicon-silicide junction.

As described above, in silicide layers 39 ₁, 39 ₂, 39 ₃, the workfunction of silicide can be modulated by the addition of a foreignelement to a certain silicide. As a result, the interface resistance isreduced at the junction of silicide and other parts.

Therefore, in the resistance change memory described in the application,the write current or read current can be supplied to the memory element20 without any current attenuation attributed to the interfaceresistance.

Furthermore, as in the example of the field effect transistor in FIG.22, silicide layers 39 ₁, 39 ₂, 39 ₃ used for the gate electrode and thesource/drain electrodes of the select transistor STr contain anadditional element, so that the agglomeration and diffusion of the metalelements included in the silicide layer caused by the high-temperaturethermal treatment are inhibited. Thus, deterioration of currenttransferring capability of the select transistor STr resulting from thehigh-temperature thermal treatment is inhibited.

Therefore, a write current of an intensity sufficient to write data intomemory element 20 can be supplied, and writing failure due to thereduction of the write current can be prevented. Moreover, the reductionof the read current due to the interface resistance can be inhibitedsimilarly to the write current, so that deterioration of a current orpotential (e.g., a bit line potential) for determining data can beinhibited, and data can be read with accuracy.

Furthermore, since the influence of the reduction of the write currentdue to the interface resistance is reduced, there is no need to generatea high current in advance to counter the reduction of the current due tohigh interface resistance. Thus, the power consumption of the resistancechange memory can be reduced.

Consequently, as shown in FIG. 24, characteristic deterioration of theelement used in the resistance change memory can also be inhibited inthe application of the embodiment.

(3) Flash Memory

In the example described above, a silicide layer including an Sielement, a 3d transition metal element and an additional element havingan atomic radius greater than the atomic radius of the 3d transitionmetal element is used for the resistance change memory.

However, this silicide layer can also be used for other semiconductormemories. The above-mentioned silicide layer can be applied to a flashmemory.

FIG. 25A and FIG. 25B show the sectional structure of one cell unit(NAND cell unit) in a NAND type flash memory. FIG. 25A shows the sectionof the NAND cell unit along a y-direction, and FIG. 25B shows thesection of the NAND cell unit along an x-direction.

One NAND cell unit comprises a plurality of memory cells MC (e.g., nmemory cells MC) having their current paths connected in series, andselect transistors SG1, SG2 connected to one end of the plurality ofmemory cells MC and the other.

As shown in FIG. 25A and FIG. 25B, the NAND cell unit is disposed in anactive area AA of a semiconductor substrate 80. The active areas AAadjacent in the x-direction are electrically isolated from each other byan element isolation insulating film 89.

As shown in FIG. 25A, a memory cell MC is a field effect transistorhaving a gate structure in which an control gate electrodes 39, 84 arestacked on a charge storage layer 82A.

The gate structure of the memory cell MC may be a stack gate structurethat uses a floating gate electrode for the charge storage layer 82A, ora MONOS structure that uses an insulating film (e.g., a silicon nitridefilm) including a trap level for the charge storage layer 82A. In thecase shown in FIG. 25A and FIG. 25B, the floating gate electrode is usedfor the charge storage layer.

The floating gate electrode 82A is provided on a gate insulating film 81formed on the surface of semiconductor substrate 80.

The control gate electrode 39, 84A are stacked on the floating gateelectrode 82A via an intergate insulating film 83A. the control gateelectrode 84A, 39 have a polycide structure in which the silicide layer39 is stacked on a polycrystalline Si layer 84A. In addition, thecontrol gate electrode may have a fully-silicided structure (FUSIstructure) in which the entire control gate electrode from its upper endto lower end is formed of a silicide layer.

The control gate electrode 39, 84A extend in the x-direction, and areshared by the plurality of memory cells MC adjacent in the x-direction.The control gate electrodes 39, 84A are used as word lines WL.

Furthermore, the plurality of memory cells MC adjacent in they-direction share diffusion layers 85A, and are connected in series. Thediffusion layer 85A is used as the source/drain of the memory cells MC.

Select transistors SG1, SG2 are provided on one end (drain side) of thememory cells MC connected in series and the other end thereof (sourceside), respectively. Select transistors SG1, SG2 are connected to theadjacent memory cells MC via diffusion layers 85D, 85S.

Select transistors SG1, SG2 are formed in a simultaneous process withthe memory cells MC, and therefore become field effect transistors ofthe stack gate structure. A lower gate electrode 82B of selecttransistors SG1, SG2 are formed simultaneously with the floating gateelectrode 82A. An upper gate electrode 39, 84B of select transistorsSG1, SG2 are formed simultaneously with the control gate electrode 39,84A. In select transistors SG1, SG2, The upper gate electrode 84B iselectrically connected to the lower gate electrode 3B via opening formedin intergate insulating film.

The upper gate electrodes 39, 84B have a polycide structure, and includethe silicide layer 39. Gate electrodes 39, 82B, 84B of selecttransistors SG1, SG2 are shared by a plurality of select transistorsadjacent in the x-direction. Gate electrodes 39, 82B, 84B of two selecttransistors SG1, SG2 are used as select gate lines.

Drain-side diffusion layer 86D of the select transistor SG1 is connectedto bit line BL via contacts BC, V1 and intermediate interconnect lineMO. Source-side diffusion layer 86S of the select transistor SG2 isconnected to a source line SL via a source line contact SC.

In addition, contacts BC, SC, V1 and interconnect lines M0, BL, SL areformed in interlayer insulating films 88A, 88B, 88C.

A method of manufacturing the flash memory according to the applicationis described next with FIG. 26.

As shown in FIG. 26, gate electrodes 82A, 84A, 82B, 84B of a memory celland select transistors are formed on the semiconductor substrate 80 bythe CVD method, photolithography and RIE method. As described above, inthe memory cell, control gate electrode 84A is formed on the floatinggate electrode 82A via the intergate insulating film 83A. The controlgate electrode 84A is made of, for example, a polycrystalline Si layer.

After gate electrodes 82A, 84A, 82B, 84B are formed, the interlayerinsulating film 88A is formed over gate electrodes 82A, 84A. Then, theinterlayer insulating film 88A is etched back, and control gateelectrode 84A and the upper part of the gate electrode 84B of the gateelectrode are exposed.

Furthermore, as in the manufacturing method shown in FIG. 14A and FIG.14B, an alloy film 59 is deposited on the interlayer insulating film 88Aand on exposed the control gate electrode 84A. The alloy film 59includes a 3d transition metal element, and an element (additionalelement) having an atomic radius greater than the atomic radius of the3d transition metal element. Then, the substrate 80 is thermallytreated, and the alloy film 59 and an upper part of the polycrystallineSi layer 84A of the control gate electrode cause a silicide reaction.

Thus, as shown in FIG. 25A and FIG. 25B, the silicide layer 39 is formedon the polycrystalline Si layer 84A of the control gate electrode. Inaddition to the Si element and the 3d transition metal element, thesilicide layer 39 includes an element having an atomic radius greaterthan the atomic radius of the 3d transition metal element.

Similarly, the silicide layer 39 is also formed on the polycrystallineSi layer 84B in the gate electrode (select gate line) of the selecttransistor.

In addition, any one of the second to fourth manufacturing methodsdescribed in Example may be used as the method of forming the silicidelayer 39 in the gate electrode of the memory cell.

After the alloy film which has not caused a silicide reaction isremoved, interlayer insulating films 88B, 88C, contacts BC, SC, V1 andinterconnect lines MO, BL, SL are sequentially formed on the substrate80 by a known technique. Thus, the flash memory shown in FIG. 25A andFIG. 25B is completed.

As described above, the silicide layer 39 including the Si element, the3d transition metal element and the additional element (foreign element)can be applied to the gate electrodes of the memory cell and the selecttransistor, that is, a control line (word line/select gate line) of theflash memory. In this silicide layer 39, the atomic radius of theadditional element is greater than the atomic radius of the 3dtransition metal element, as in the silicide layer used in theresistance change memory.

This makes it possible to reduce the interface resistance of thesilicon-silicide junction in the word line WL.

In the write operation of the flash memory, a write voltage is appliedto the selective word line in the selected cell unit, so that a chargeis injected into the charge storage layer 82A.

According to the application, since the reduction of the write voltageresulting from the interface resistance is small in the word line(control gate electrode) having the polycide structure, there is no needto generate a high voltage in advance to counter the reduction of thewrite voltage due to the interface resistance. Thus, the powerconsumption of the flash memory can be reduced.

While the flash memory has been described herein by way of example, thesilicide layer 39 described in the embodiment can be applied to a DRAMor SRAM or to a mixed memory including the former memories. In the DRAMor SRAM, the silicide layer described in the present embodiment is usedfor the gate electrode (word line) or the source/drain electrodes of thetransistor included in the memory cell.

[Others]

While certain embodiments have been described, these embodiments havebeen presented by way of example only, and are not intended to limit thescope of the inventions. Indeed, the novel embodiments described hereinmay be embodied in a variety of other forms; furthermore, variousomissions, substitutions and changes in the form of the embodimentsdescribed herein may be made without departing from the spirit of theinventions. The accompanying claims and their equivalents are intendedto cover such forms or modifications as would fall within the scope andspirit of the inventions.

1-13. (canceled)
 14. A resistance change memory manufacturing methodcomprising: forming, above a substrate, a semiconductor layer includingSi; forming a metal film on the semiconductor layer, the metal filmincluding a 3d transition metal element having a first atomic radius,and at least one kind of an additional element having a second atomicradius greater than the first atomic radius; and performing the metalfilm to a thermal treatment at 500° C. or more to form a silicide layerincluding the 3d transition metal element and the additional element onthe semiconductor layer.
 15. The resistance change memory manufacturingmethod according to claim 14, further comprising: depositing aresistance change layer, and forming a cell unit which comprises anon-ohmic element including the silicide layer and a memory elementincluding the resistance change film.
 16. A resistance change memorymanufacturing method comprising: forming a semiconductor layer includingSi on above a substrate; forming, on the semiconductor layer, a silicidelayer, and a 3d transition metal element having a first atomic radius;adding at least one kind of an additional element having a second atomicradius greater than the first atomic radius into the silicide layer byion implantation; and forming a cell unit which comprises a non-ohmicelement including the silicide layer to which the additional element isadded and a memory element including a resistance change film.
 17. Theresistance change memory manufacturing method according to claim 16,wherein the ion implantation is carried out after the semiconductorlayer containing Si is processed.